Furthering a partnership: Air quality modeling and improving public health.

Air pollution is one of the top five risk factors for population health globally. In recent years, advances in air pollution data and modeling have occurred simultaneously with advances in data and methods available for health studies. To realize the potential of such advances, the air quality modeling and public health communities should continue to strengthen their engagements and build effective interdisciplinary teams. These partnerships recognize the tight coupling between air quality and health data and methods and the value of expertise from multiple fields to ensure that this information is applied appropriately with a deep understanding of its capabilities and limitations. Building effective multidisciplinary teams takes a sustained commitment to engage with partners with different expertise to establish working partnerships and collaborations to better address public exposures to air pollution. Effective partnerships enable better targeting of research resources to answer important questions and provide essential information to protect public health.Implications: Air quality models are an effective tool that can be used to estimate air pollution exposure in epidemiologic studies and risk assessments. Working together in collaborative multidisciplinary teams will lead to greater advancements in understanding of air pollution impacts and in useful information informing actions to improve public health.

Reflecting on progress since the 2005 NARSTO emissions inventory report.

Emission inventories are the foundation for cost-effective air quality management activities. In 2005, a report by the public/private partnership North American Research Strategy for Tropospheric Ozone (NARSTO) evaluated the strengths and weaknesses of North American emissions inventories and made recommendations for improving their effectiveness. This paper reviews the recommendation areas and briefly discusses what has been addressed, what remains unchanged, and new questions that have arisen. The findings reveal that all emissions inventory improvement areas identified by the 2005 NARSTO publication have been explored and implemented to some degree. The U.S. National Emissions Inventory has become more detailed and has incorporated new research into previously under-characterized sources such as fine particles and biomass burning. Additionally, it is now easier to access the emissions inventory and the documentation of the inventory via the internet. However, many emissions-related research needs exist, on topics such as emission estimation methods, speciation, scalable emission factor development, incorporation of new emission measurement techniques, estimation of uncertainty, top-down verification, and analysis of uncharacterized sources. A common theme throughout this retrospective summary is the need for increased coordination among stakeholders. Researchers and inventory developers must work together to ensure that planned emissions research and new findings can be used to update the emissions inventory. To continue to address emissions inventory challenges, industry, the scientific community, and government agencies need to continue to leverage resources and collaborate as often as possible. As evidenced by the progress noted, continued investment in and coordination of emissions inventory activities will provide dividends to air quality management programs across the country, continent, and world. Implications: In 2005, a report by the public/private partnership North American Research Strategy for Tropospheric Ozone (NARSTO) evaluated the strengths and weaknesses of North American air pollution emissions inventories. This paper reviews the eight recommendation areas and briefly discusses what has been addressed, what remains unchanged, and new questions that have arisen. Although progress has been made, many opportunities exist for the scientific agencies, industry, and government agencies to leverage resources and collaborate to continue improving emissions inventories.

Controlling Biogenic Particle Mass with NOx and SOx.

Models that accurately predict atmospheric composition and correctly respond to tested policy scenarios aid air quality managers in the development of effective strategies to protect human health. Controllable emissions from human activity interact with natural emissions from plants and trees from the biosphere through complex chemistry to form ozone (O3) and organic fine particulate matter (PM2.5), criteria air pollutants that induce a variety of adverse health effects. While organic gases emitted from plants and trees are natural, some fraction of the subsequent O3 and PM2.5 is not. Accurate assessment of the extent to which human activity and natural emissions interact to form pollution can be achieved when models are constructed from first principle chemical and physical laws, and tested and evaluated with laboratory and field observations. In the summer of 2013, hundreds of scientists descended on the southeast U.S. to coordinate an atmospheric chemistry campaign with the ultimate goal of understanding complex biosphere-atmosphere interactions, the subsequent formation of O3 and PM2.5, and accurate incorporation of the chemistry into atmospheric models. A main finding from the campaign is that anthropogenic emissions facilitate formation of organic PM2.5 derived from biogenic VOCs. This fraction of PM2.5 is controllable pollution. Mechanistic insight from that campaign was recently incorporated into EPA's air quality model, improving the model representation of the atmospheric modeling and informing air quality management strategies for PM2.5. Emission reductions in SO2 and NOx in the southeast U.S. are found to reduce non-fossil, presumably biogenic, organic PM2.5 mass concentrations, suggesting existing Federal rules have been more successful than anticipated. Additional potential feedback mechanisms may become important as emissions reductions bring the atmosphere into new chemical regimes.

Synthesizing scientific progress: outcomes from U.S. EPA's carbonaceous aerosols and source apportionment STAR grants.

In response to recommendations by the National Research Council in the late 1990 s and early 2000s for critical research into understanding sources and formation mechanisms of PM2.5, EPA created multiple funding opportunities through the Science to Achieve Results (STAR) program: "Measurement, Modeling, and Analysis Methods for Airborne Carbonaceous Fine Particulate Matter" (2003) and "Source Apportionment of Particulate Matter" (2004). The carbonaceous fine PM solicitation resulted in 16 different projects focusing on the measurement methods, source identification, and exploration of the chemical and physical processes important for PM2.5 carbon in the atmosphere. The source apportionment funding opportunity led to 11 projects improving tools and characterization of source-receptor relationships of PM2.5. Many funding mechanisms include a final synopsis of funded research and published manuscripts. Here, this evaluation is extended to include citations of research published as part of these solicitations. These solicitations resulted in 275 publications that included more than 850 unique authors in 37 different journals with a weighted average 2011 impact factor of 4.21. At the time of this assessment, these publications have been cited by 13,612 peer review journal articles with 31 (11%) of the manuscripts being cited over 100 times.

Updating the conceptual model for fine particle mass emissions from combustion systems.

Atmospheric transformations determine the contribution of emissions from combustion systems to fine particulate matter (PM) mass. For example, combustion systems emit vapors that condense onto existing particles or form new particles as the emissions are cooled and diluted. Upon entering the atmosphere, emissions are exposed to atmospheric oxidants and sunlight, which causes them to evolve chemically and physically, generating secondary PM. This review discusses these transformations, focusing on organic PM. Organic PM emissions are semi-volatile at atmospheric conditions and thus their partitioning varies continuously with changing temperature and concentration. Because organics contribute a large portion of the PM mass emitted by most combustion sources, these emissions cannot be represented using a traditional, static emission factor. Instead, knowledge of the volatility distribution of emissions is required to explicitly account for changes in gas-particle partitioning. This requires updating how PM emissions from combustion systems are measured and simulated from combustion systems. Secondary PM production often greatly exceeds the direct or primary PM emissions; therefore, secondary PM must be included in any assessment of the contribution of combustion systems to ambient PM concentrations. Low-volatility organic vapors emitted by combustion systems appear to be very important secondary PM precursors that are poorly accounted for in inventories and models. The review concludes by discussing the implications that the dynamic nature of these PM emissions have on source testing for emission inventory development and regulatory purposes. This discussion highlights important linkages between primary and secondary PM, which could lead to simplified certification test procedures while capturing the emission components that contribute most to atmospheric PM mass.

Influence of a polar near-neighbor on incipient proton transfer in a strongly hydrogen bonded complex.

Rotational spectroscopy and ab initio calculations have been used to characterize the complexes H(3)N-HF and H(3)N-HF-HF in the gas phase. H(3)N-HF is a C(3v) symmetric, hydrogen bonded system with an NF distance of 2.640(21) A and an N...H hydrogen bond length of 1.693(42) A. The H(3)N-HF-HF complex, on the other hand, forms a six-membered HN-HF-HF ring, in which both the linear hydrogen bond in the H(3)N-HF moiety and the F-H-F angle of (HF)(2) are perturbed relative to those in the corresponding dimers. The N...F and F...F distances in the trimer are 2.4509(74) A and 2.651(11) A, respectively. The N...H hydrogen bond length in H(3)N-HF-HF is 1.488(12) A, a value which is 0.205(54) A shorter than that in H(3)N-HF. Similarly, the F...F distance, 2.651(11) A, is 0.13(2) A shorter than that in (HF)(2). Counterpoise-corrected geometry optimizations are presented, which are in good agreement with the experimental structures for both the dimer and trimer, and further characterize small, but significant, changes in the NH(3) and HF subunits upon complexation. Analysis of internal rotation in the spectrum of H(3)N-HF-HF gives the potential barrier for internal rotation of the NH(3) unit, V(3), to be 118(2) cm(-1). Ab initio calculations reproduce this number to within 10% if the monomer units and the molecular frame are allowed to fully relax as the internal rotation takes place. The binding energies of H(3)N-HF and H(3)N-HF-HF, calculated at the MP2/aug-cc-pVTZ level and corrected for basis set superposition error are 12.3 and 22.0 kcal/mol, respectively. Additional energy calculations have been performed to explore the lowest frequency vibration of H(3)N-HF-HF, a ring-opening motion that increases the NFF angle. The addition of one HF molecule to H(3)N-HF represents the first step of microsolvation of a hydrogen bonded complex and the results of this study demonstrate that a single, polar near-neighbor has a significant influence on the extent of proton transfer across the hydrogen bond. As measured using the proton-transfer parameter rho(PT), previously defined by Kurnig and Scheiner [Int. J. Quantum Chem., Quantum Biol. Symp. 1987, 14, 47], the degree of proton transfer in H(3)N-HF-HF is greater than that in either (CH(3))(3)N-HF or H(3)N-HCl but less than that in (CH(3))(3)N-HCl.

Reactions at interfaces as a source of sulfate formation in sea-salt particles.

Understanding the formation of sulfate particles in the troposphere is critical because of their health effects and their direct and indirect effects on radiative forcing, and hence on climate. Laboratory studies of the chemical and physical changes in sodium chloride, the major component of sea-salt particles, show that sodium hydroxide is generated upon reaction of deliquesced sodium chloride particles with gas-phase hydroxide. The increase in alkalinity will lead to an increase in the uptake and oxidation of sulfur dioxide to sulfate in sea-salt particles. This chemistry is missing from current models but is consistent with a number of previously unexplained field study observations.

Microwave investigation of sulfuric acid monohydrate.

The complex H2SO4-H2O has been observed by rotational spectroscopy in a supersonic jet. A-type spectra for 18 isotopic forms have been analyzed, and the vibrationally averaged structure of the system has been determined. The complex forms a distorted, six-membered ring with the water unit acting as both a hydrogen bond donor and a hydrogen bond acceptor toward the sulfuric acid. One of the H2SO4 protons forms a short, direct hydrogen bond to the water oxygen, with an H...O distance of 1.645(5) A and an O-H...O angle of 165.2(4) degrees. Additionally, the orientation of the water suggests a weaker, secondary hydrogen bond between one of the H2O hydrogens and a nearby S=O oxygen on the sulfuric acid, with an O...H distance of 2.05(1) A and an O-H...O angle of 130.3(5) degrees. The experimentally determined structure is in excellent agreement with previously published DFT studies. Experiments with HOD in the jet reveal the formation of only isotopomers involving deuterium in the secondary hydrogen bond, providing direct experimental evidence for the secondary H...O interaction. Extensive isotopic substitution has also permitted a re-determination of the structure of the H2SO4 unit within the complex. The hydrogen-bonding OH bond of the sulfuric acid elongates by 0.07(2) A relative to that in free H2SO4, and the S=O bond involved in the secondary interaction stretches by 0.04(1) A. These changes reflect substantial distortion of the H2SO4 moiety in response to only a single water molecule, and prior to the proton transfer event. Spectral data indicate that the complex undergoes at least one, and probably more than one type of internal motion. Although the sulfuric acid in this work was produced from direct reaction of SO3 and water in the jet, experiments with H2(18)O indicate that about 2-3% of the acid is formed via processes not normally associated with the gas-phase hydration of SO3.