Modeling the Current and Future Roles of Particulate Organic Nitrates in the Southeastern United States.

Organic nitrates are an important aerosol constituent in locations where biogenic hydrocarbon emissions mix with anthropogenic NOx sources. While regional and global chemical transport models may include a representation of organic aerosol from monoterpene reactions with nitrate radicals (the primary source of particle-phase organic nitrates in the Southeast United States), secondary organic aerosol (SOA) models can underestimate yields. Furthermore, SOA parametrizations do not explicitly take into account organic nitrate compounds produced in the gas phase. In this work, we developed a coupled gas and aerosol system to describe the formation and subsequent aerosol-phase partitioning of organic nitrates from isoprene and monoterpenes with a focus on the Southeast United States. The concentrations of organic aerosol and gas-phase organic nitrates were improved when particulate organic nitrates were assumed to undergo rapid (τ = 3 h) pseudohydrolysis resulting in nitric acid and nonvolatile secondary organic aerosol. In addition, up to 60% of less oxidized-oxygenated organic aerosol (LO-OOA) could be accounted for via organic nitrate mediated chemistry during the Southern Oxidants and Aerosol Study (SOAS). A 25% reduction in nitrogen oxide (NO + NO2) emissions was predicted to cause a 9% reduction in organic aerosol for June 2013 SOAS conditions at Centreville, Alabama.

Development of a database for chemical mechanism assignments for volatile organic emissions.

UNLABELLED: The development of a database for making model species assignments when preparing total organic gas (TOG) emissions input for atmospheric models is described. This database currently has assignments of model species for 12 different gas-phase chemical mechanisms for over 1700 chemical compounds and covers over 3000 chemical categories used in five different anthropogenic TOG profile databases or output by two different biogenic emissions models. This involved developing a unified chemical classification system, assigning compounds to mixtures, assigning model species for the mechanisms to the compounds, and making assignments for unknown, unassigned, and nonvolatile mass. The comprehensiveness of the assignments, the contributions of various types of speciation categories to current profile and total emissions data, inconsistencies with existing undocumented model species assignments, and remaining speciation issues and areas of needed work are also discussed. The use of the system to prepare input for SMOKE, the Speciation Tool, and for biogenic models is described in the supplementary materials. The database, associated programs and files, and a users manual are available online at http://www.cert.ucr.edu/~carter/emitdb . IMPLICATIONS: Assigning air quality model species to the hundreds of emitted chemicals is a necessary link between emissions data and modeling effects of emissions on air quality. This is not easy and makes it difficult to implement new and more chemically detailed mechanisms in models. If done incorrectly, it is similar to errors in emissions speciation or the chemical mechanism used. Nevertheless, making such assignments is often an afterthought in chemical mechanism development and emissions processing, and existing assignments are usually undocumented and have errors and inconsistencies. This work is designed to address some of these problems.

Secondary organic aerosol from ozonolysis of biogenic volatile organic compounds: chamber studies of particle and reactive oxygen species formation.

The formation of secondary organic aerosol (SOA) produced from α-pinene, linalool, and limonene by ozonolysis was examined using a dynamic chamber system that allowed the simulation of ventilated indoor environments. Experiments were conducted at typical room temperatures and air exchange rates. Limonene ozonolysis produced the highest SOA mass concentrations and linalool the lowest with α-pinene being intermediate. Simplified empirical modeling simulations were conducted to provide insights into reaction chemistry. Assessment of variability of particle-bound reactive oxygen species (ROS) may be important in the understanding of health effects associated with particulate matter. The ROS intensities defined as ROS/SOA mass were found to be moderately correlated with the SOA densities. Greater ROS intensities were observed for the cases where ozone was in excess. ROS intensities approached a relatively constant value in the region where ozone was in deficit. The estimated initial ROS half-life time was approximately 6.5 h at room temperature suggesting the time sensitivity of ROS measurements. The ROS formed from terpenoid ozonolysis could be separated into three categories: short-lived/high reactive/volatile, semivolatile/relatively stable and nonvolatile/low reactive species based on ROS measurements under various conditions. Such physical characterization of the ROS in terms of reactivity and volatility provides some insights into the nature of ROS.

Reactivity scales as comparative tools for chemical mechanisms.

Incremental ozone impacts or reactivities have been calculated for selected organic compounds using a Master Chemical Mechanism (MCMv3.1) and compared with those calculated elsewhere with the SAPRC-07 chemical mechanism. The comparison of incremental reactivities has been completed for 116 organic compounds representing the alkanes, alkenes, aldehydes, ketones, aromatics, oxygenates, and halocarbons. Both mechanisms have constructed a consistent and coherent description of reactivity within each class of organics. MCMv3.1 and SAPRC-07 have represented some features of the available body of understanding concerning the atmospheric oxidation of organic compounds in a consistent and quantitative manner, although significant differences were found for 14 organic compounds. These differences represent species-dependent facets of their atmospheric chemistry that have not been adequately resolved in the available literature experimental data.

Updating the SAPRC Maximum Incremental Reactivity (MIR) scale for the United States from 1988 to 2010.

Ozone reactivity scales play an important role in selecting which chemical compounds are used in products ranging from gasoline to pesticides to hairspray in California, across the United States and around the world. The California Statewide Air Pollution Research Center (SAPRC) box model that calculates ozone reactivity uses a representative urban atmosphere to predict how much additional ozone forms for each kilogram of compound emission. This representative urban atmosphere has remained constant since 1988, even though more than 25 years of emissions controls have greatly reduced ambient ozone concentrations across the United States during this time period. Here we explore the effects of updating the representative urban atmosphere used for ozone reactivity calculations from 1988 to 2010 conditions by updating the meteorology, emission rates, concentration of initial conditions, concentration of background species, and composition of volatile organic compound (VOC) profiles. Box model scenarios are explored for 39 cities across the United States to calculate the Maximum Incremental Reactivity (MIR) scale for 1,233 individual compounds and compound-mixtures. Median MIR values across the cities decreased by approximately 20.3% when model conditions were updated. The decrease is primarily due to changes in atmospheric composition ultimately attributable to emissions control programs between 1998 and 2010. Further effects were caused by changes in meteorological variables stemming from shifting seasons for peak ozone events (summer versus early fall). Lumped model species with the highest MIR values in 1988 experienced the greatest decrease in MIR values when conditions were updated to 2010. Despite the reduction in the absolute reactivity in the updated 2010 atmosphere, the relative ranking of the VOCs according to their reactivity did not change strongly compared to the original 1988 atmosphere. These findings indicate that past decisions about ozone control programs remain valid today, and the ozone reactivity scale continues to provide relevant guidance for future policy decisions even as new products are developed. Implications: Updating the representative urban atmosphere used for the Maximum Incremental Reactivity (MIR) scale from 1988 to 2010 conditions caused the reactivity of 1223 individual compounds and combined mixtures to decrease by an average of 20.3% but the relative ranking of the VOCs was not strongly affected. This means that previous guidance about preferred chemical formulations to reduce ozone formation in cities across the United States remain valid today, and the MIR scale continues to provide relevant guidance for future policy decisions even as new products are developed.

The ozone formation potential of 1-bromo-propane.

1-Bromo-propane (1-BP) is a replacement for high-end chlorofluorocarbon (HCFC) solvents. Its reaction rate constant with the OH radical is, on a weight basis, significantly less than that of ethane. However, the overall smog formation chemistry of 1-BP appears to be very unusual compared with typical volatile organic compounds (VOCs) and relatively complex because of the presence of bromine. In smog chamber experiments, 1-BP initially shows a faster ozone build-up than what would be expected from ethane, but the secondary products containing bromine tend to destroy ozone such that 1-BP can have a net overall negative reactivity. Alternative sets of reactions are offered to explain this unusual behavior. Follow-up studies are suggested to resolve the chemistry. Using one set of bromine-related reactions in a photochemical grid model shows that 1-BP would be less reactive toward peak ozone formation than ethane with a trend toward even lower ozone impacts in the future.

Rate of gas phase association of hydroxyl radical and nitrogen dioxide.

The reaction of OH and NO(2) to form gaseous nitric acid (HONO(2)) is among the most influential in atmospheric chemistry. Despite its importance, the rate coefficient remains poorly determined under tropospheric conditions because of difficulties in making laboratory rate measurements in air at 760 torr and uncertainties about a secondary channel producing peroxynitrous acid (HOONO). We combined two sensitive laser spectroscopy techniques to measure the overall rate of both channels and the partitioning between them at 25°C and 760 torr. The result is a significantly more precise value of the rate constant for the HONO(2) formation channel, 9.2 (±0.4) × 10(-12) cm(3) molecule(-1) s(-1) (1 SD) at 760 torr of air, which lies toward the lower end of the previously established range. We demonstrate the impact of the revised value on photochemical model predictions of ozone concentrations in the Los Angeles airshed.