Browsing by Author "Capps, Shannon L."
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- Coupling of organic and inorganic aerosol systems and the effect on gas-particle partitioning in the southeastern USPye, Havala O. T.; Zuend, Andreas; Fry, Juliane L.; Isaacman-VanWertz, Gabriel; Capps, Shannon L.; Appel, K. Wyat; Foroutan, Hosein; Xu, Lu; Ng, Nga L.; Goldstein, Allen H. (European Geophysical Union, 2018-01-12)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 x sulfate, R-N/2S approximate to 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 mu g m(-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 levoglucosan but decrease particle-phase partitioning for low O : C, monoterpene-derived species.
- Evaluating oil and gas contributions to ambient nonmethane hydrocarbon mixing ratios and ozone-related metrics in the Colorado Front RangeLyu, Congmeng; Capps, Shannon L.; Kurashima, Kent; Henze, Daven K.; Pierce, Gordon; Hakami, Amir; Zhao, Shunliu; Resler, Jaroslav; Carmichael, Gregory R.; Sandu, Adrian; Russell, Armistead G.; Chai, Tianfeng; Milford, Jana (2021-02-01)Recently, oil and natural gas (O&NG) production activities in the Denver-Julesburg Basin have expanded rapidly. Associated nonmethane hydrocarbon (NMHC) emissions contribute to photochemical formation of ground-level ozone and include benzene as well as other hazardous air pollutants. Using positive matrix factorization (PMF) and chemical mass balance (CMB) methods, we estimate how much O&NG activities and other sources contribute to morning NMHC mixing ratios measured from 2013 to mid-2016 at a site in Platteville, CO, in the Denver-Julesburg Basin, and at a contrasting site in downtown Denver. A novel adjoint sensitivity analysis method is then used to estimate corresponding contributions to ozone and ozone-linked mortality in the Denver region. Average 6-9 am NMHC mixing ratios in Platteville were seven times higher than those in Denver in 2013 but four times higher in 2016. CMB estimates that O&NG activities contributed to the Platteville (Denver) site an average of 96% (56%) of NMHC on a carbon basis while PMF indicated 92% (33%). Average vehicle-related contributions of NMHC are estimated as 41% by CMB and 53% by PMF in Denver. Estimates of the fractional contribution to potential ozone and ozone-linked mortality from O&NG activities are smaller while those from vehicles are larger than the NMHC contributions. CMB (PMF) indicate that greater than 78% (40%) of annual average benzene in Denver is attributable to vehicle emissions while greater than 75% (67%) of benzene in Platteville is attributable to O&NG activities.