Global modeling of SOA: the use of different mechanisms for aqueous-phase formation

There is growing interest in the formation of secondary organic aerosol (SOA) through condensed aqueous-phase reactions. In this study, we use a global model (IMPACT) to investigate the potential formation of SOA in the aqueous phase. We compare results from several multiphase process schemes with detailed aqueous-phase reactions to schemes that use a first-order gas-to-particle formation rate based on uptake coefficients. The predicted net global SOA production rate in cloud water ranges from 13.1 Tg yr-1 to 46.8 Tg yr-1 while that in aerosol water ranges from -0.4 Tg yr-1 to 12.6 Tg yr-1. The predicted global burden of SOA formed in the aqueous phase ranges from 0.09 Tg to 0.51 Tg. A sensitivity test to investigate two representations of cloud water content from two global models shows that increasing cloud water by an average factor of 2.7 can increase the net SOA production rate in cloud water by a factor of 4 at low altitudes (below approximately 900 hPa). We also investigated the importance of including dissolved Fe chemistry in cloud water aqueous reactions. Adding these reactions increases the formation rate of aqueous-phase OH by a factor of 2.6 and decreases the amount of global aqueous SOA formed by 31%. None of the mechanisms discussed here is able to provide a best fit for all observations. Rather, the use of an uptake coefficient method for aerosol water and a multi-phase scheme for cloud water provides the best fit in the Northern Hemisphere and the use of multiphase process scheme for aerosol and cloud water provides the best fit in the tropics. The model with Fe chemistry underpredicts oxalate measurements in all regions. Finally, the comparison of oxygen-to-carbon (O / C) ratios estimated in the model with those estimated from measurements shows that the modeled SOA has a slightly higher O / C ratio than the observed SOA for all cases

Effects of cloud overlap in photochemical models

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95365/1/jgrd10939.pd

O 3 ‐NO x ‐VOC sensitivity and NO x ‐VOC indicators in Paris: Results from models and Atmospheric Pollution Over the Paris Area (ESQUIF) measurements

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/94641/1/jgrd9597.pd

Some theoretical results concerning O 3 ‐NO x ‐VOC chemistry and NO x ‐VOC indicators

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/94731/1/jgrd9243.pd

Radiative forcing of organic aerosol in the atmosphere and on snow: Effects of SOA and brown carbon

Organic aerosols (OA) play an important role in climate change. However, very few calculations of global OA radiative forcing include secondary organic aerosol (SOA) or the light‐absorbing part of OA (brown carbon). Here we use a global model to assess the radiative forcing associated with the change in primary organic aerosol (POA) and SOA between present‐day and preindustrial conditions in both the atmosphere and the land snow/sea ice. Anthropogenic emissions are shown to substantially influence the SOA formation rate, causing it to increase by 29 Tg/yr (93%) since preindustrial times. We examine the effects of varying the refractive indices, size distributions for POA and SOA, and brown carbon fraction in SOA. The increase of SOA exerts a direct forcing ranging from −0.12 to −0.31 W m −2 and a first indirect forcing in warm‐phase clouds ranging from −0.22 to −0.29 W m −2 , with the range due to different assumed SOA size distributions and refractive indices. The increase of POA since preindustrial times causes a direct forcing varying from −0.06 to −0.11 W m −2 , when strongly and weakly absorbing refractive indices for brown carbon are used. The change in the total OA exerts a direct forcing ranging from −0.14 to −0.40 W m −2 . The atmospheric absorption from brown carbon ranges from +0.22 to +0.57 W m −2 , which corresponds to 27%~70% of the black carbon (BC) absorption predicted in the model. The radiative forcing of OA deposited in land snow and sea ice ranges from +0.0011 to +0.0031 W m −2 or as large as 24% of the forcing caused by BC in snow and ice simulated by the model. Key Points A fully explicit SOA formation model is used to determine SOA radiative forcing The direct radiative forcing by brown carbon in SOA is estimated The radiative forcing of OA in snow/ice is estimated for the first timePeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/108060/1/jgrd51450.pd

Dependence of ozone production on NO and hydrocarbons in the troposphere

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95525/1/grl10419.pd

Observed suppression of ozone formation at extremely high temperatures due to chemical and biophysical feedbacks

Ground level ozone concentrations ([O3]) typically show a direct linear relationship with surface air temperature. Three decades of California measurements provide evidence of a statistically significant change in the ozone-temperature slope (ΔmO3-T) under extremely high temperatures (> 312 K). This ΔmO3-T leads to a plateau or decrease in [O3], reflecting the diminished role of nitrogen oxide sequestration by peroxyacetyl nitrates and reduced biogenic isoprene emissions at high temperatures. Despite inclusion of these processes in global and regional chemistry-climate models, a statistically significant change in ΔmO3-T has not been noted in prior studies. Future climate projections suggest a more frequent and spatially widespread occurrence of this ΔmO3-T response, confounding predictions of extreme ozone events based on the historically observed linear relationship

The Sensitivity of U.S. Surface Ozone Formation to NOx, and VOCs as Viewed from Space

We investigated variations in the sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NO(x)) as inferred from the ratio of tropospheric columns of formaldehyde and nitrogen dioxide from the Aura Ozone Monitoring Instrument (OMI). The data indicate that ozone formation became: 1. more sensitive to NO(x) over most of the U.S, from 2005 to 2007 because of substantial decreases in NO(x) emissions primarily from stationary sources, and 2. more sensitive to NO(x) with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. Based on our interpretation of the data, current strategies implemented to reduce unhealthy levels of surface ozone should focus more on reducing NO(x) emissions, except in some downtown areas which have historically benefited from reductions in VOC emissions

Application of OMI Observations to a Space-Based Indicator of NOx and VOC Controls on Surface Ozone Formation

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NOx) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the "Ratio") from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios less than 1 and NOx at Ratios greater than 2; both NOx and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria. the OMI data indicate that ozone formation became: 1. more sensitive to NOx over most of the United States from 2005 to 2007 because of the substantial decrease in NOx emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO2. and 2. more sensitive to NOx with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g .. Chicago). the data clearly indicate that ozone formation became more sensitive to NOx from 2005 to 2007. In cities with relatively high isoprene emissions (e.g ., Atlanta), we found that the increase in the Ratio due to decreasing NOx emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration

Factors regulating ozone over the United States and its export to the global atmosphere

The factors regulating summertime O3 over the United States and its export to the global atmosphere are examined with a 3-month simulation using a continental scale, three-dimensional photochemical model. It is found that reducing NOx emissions by 50% from 1985 levels would decrease rural O3 concentrations over the eastern United States by about 15% under almost all meteorological conditions, while reducing anthropogenic hydrocarbon emissions by 50% would have less than a 4% effect except in the largest urban plumes. The strongly NOx-limited conditions in the model reflect the dominance of rural areas as sources of O3 on the regional scale. The correlation between O3 concentrations and temperature observed at eastern U.S. sites is attributed in part to the association of high temperatures with regional stagnation, and in part to an actual dependence of O3 production on temperature driven primarily by conversion of NOx to peroxyacetylnitrate (PAN). The net number of O3 molecules produced per molecule of NOx consumed (net O3 production efficiency, accounting for both chemical production and chemical loss of O3) has a mean value of 6.3 in the U.S. boundary layer; it is 3 times higher in the western United States than in the east because of lower NOx concentrations in the west. Approximately 70% of the net chemical production of O3 in the U.S. boundary layer is exported (the rest is deposited). Only 6% of the NOx emitted in the United States is exported out of the U.S. boundary layer as NOx or PAN, but this export contributes disproportionately to total U.S. influence on global tropospheric O3because of the high O3 production efficiency per unit NOx in the remote troposphere. It is estimated that export of U.S. pollution supplies 8 Gmol O3 d−1 to the global troposphere in summer, including 4 Gmol d−1 from direct export of O3 out of the U.S. boundary layer and 4 Gmol d−1 from production of O3 downwind of the United States due to exported NOx. This U.S. pollution source can be compared to estimates of 18–28 Gmol d−1 for the cross-tropopause transport of O3 over the entire northern hemisphere in summer