Aerosol from Organic Nitrogen in the Southeast United States Office of Research and Development National Exposure Research Laboratory, United States Environmental Protection Agency CMAS Conference, 5 October 2015 Havala O. T. Pye, 1,* Deborah J. Luecken, 1 Lu Xu, 2 Christopher M. Boyd, 2 Nga L. Ng, 2 Kirk Baker, 3 Benjamin R. Ayres, 4 Jesse O. Bash, 1 Karsten Baumann, 5 William P. L. Carter, 6 Eric Edgerton, 5 Juliane L. Fry, 4 William T. Hutzell, 1 Donna Schwede, 1 and Paul B. Shepson 7 1 National Exposure Research Laboratory, US Environmental Protection Agency 2 Georgia Institute of Technology 3 Office of Air Quality Planning and Standards, US Environmental Protection Agency 4 Reed College 5 Atmospheric Research and Analysis, Inc., 6 Center for Environmental Research and Technology, University of California at Riverside 7 Purdue University *pye.havala.AT. epa.gov

Particle-phase organic nitrogen (pON) Organic nitrogen (ON) –Forms in the gas phase when VOCs react with OH/NO or the nitrate radical (NO 3 ) –Has uncertain fate (photolysis, partitioning to the particle, hydrolysis, or deposition) with implications for NO x and ozone In the particle phase, ON is an important component of PM in California, Colorado, the Southeast United States, as well as other locations 1 Carlton et al., SOAS white paper Southern Oxidant and Aerosol Study (SOAS) 1 June to 15 July 2013 Centreville, AL SEARCH network site Regionally representative NO 2 column density

Xu et al PNAS Organic aerosol in the Southeast Less oxidized-oxygenated organic aerosol (LO-OOA) Factor resolved in ambient AMS data (Xu et al PNAS) Second largest contributor to brown carbon absorption (after biomass burning) (Washenfelder et al GRL) Similar to  -pinene + NO 3 laboratory-based factor (Boyd et al ACP) Correlates with organic nitrate functional groups in the particle (R=0.81) Includes SOA from monoterpenes + NO 3 and isoprene and other minor contributions 2

Traditional BVOC+NO 3 OA model (CMAQ v5.1) + NO 3 + OH Isoprene Emission SV_ISO1 SV_ISO2 AISO1 AISO2 Monoterpenes Emission SV_TRP1 SV_TRP2 ATRP1 ATRP2 oligomers Monoterpenes: Carlton et al ES&T Isoprene: v5.1 unpublished + NO 3 + OH + Ozone 3

Revised organic nitrogen SOA model (CMAQ v5.1 saprc07tic aero6i) Aerosol Organic Nitrate Gas organic nitrate deposition Photolysis or chemical reaction deposition BVOC + NO 3 BVOC + OH, NO NO x Hydrolysis HNO 3 + Organic HNO 3 deposition 4 Benefits Interaction of aerosol system with gas system (implications for NO x, ozone) Provides more opportunities for evaluation  

What is hydrolysis? Hydrolysis is a reaction with water in the particle The organic product of hydrolysis is likely an alcohol (-ONO 2 replaced with -OH) Converts organic nitrogen (aka organic nitrates, alkyl nitrates, AN) to HNO 3 thus serves as a NO x sink Rate is likely a function of acidity and type of nitrate group (primary, secondary, tertiary) Two different implementations of hydrolysis in CMAQv5.1 cb05e51 (Pleim presentation) Similar to CB6r3, CAMx v6.1 approach Particle-NTR  HNO 3,  = 6 hrs No tracking of particle-phase NTR saprc07tic with aero6i (this work) Particle-phase biogenic organic nitrates converted to nonvolatile SOA and HNO 3 Timescale of 3 hours (30 hours as a sensitivity) Optimal timescale is faster than cb05e51, but applies to a smaller subset of organic nitrates 5

Semivolatile BVOC-nitrates Organic Nitrate Parent VOC Surrogate Structure Molec. Wt. [g/mol] O:COM/ OC Vapor Pressure [Pa] at 298 K Saturation concentration C* [  g/m 3 ] at 298K Lifetime against particle-phase hydrolysis MTNO 3 Mono- terpenes (excl. a- pinene) C 10 H 17 O 5 N231 (Fry et al. 2009) x10 -4 (Fry et al. 2009) 12 (calculated from p vap ) 3 hrs (Boyd et al. ACP 2015 for tertiary monoterpene nitrates) ISOPNNisopreneC 5 H 10 O 8 N (Rollins et al. 2009) x10 -5 (Rollins et al. 2009) 8.9 (Rollins et al. 2009) 3 hrs (Boyd et al. ACP 2015 for tertiary monoterpene nitrates) ISOPNN only has nocturnal (from reaction with NO 3 ) sources and is primarily composed of dinitrates MTNO 3 has both daytime (from RO 2 +NO) and nighttime (from NO 3 ) sources and both single and dinitrates 6

NO 3 is the dominant ON source 7 MTNO 3 Production * CIMS signal is one subset of MTNO 3 *

Monoterpene-ON SOA > Isoprene-ON SOA Monoterpene-ON SOAIsoprene-ON SOAHydrolysis Product All units:  g m -3  hydrolysis =3 hr 8

Regional BVOC SOA increases Base Biogenic SOA (v5.1 aero6)*Increase over Base All units:  g m -3 9  hydrolysis =3 hr * Base biogenic SOA: Semivolatile SOA and oligomers from monoterpenes, isoprene, sesquiterpenes following Carlton et al and IEPOX SOA following Pye et al

OC predicted at CTR June 2013 Base v5.1-beta Revised w/  hydrolysis =30 hrRevised w/  hydrolysis =3 hr Local Hour OC  gC/m 3 10 Observations CMAQ Observations CMAQ Bias in OA vs AMS: -23% (-1.26  g/m 3 ) Bias in OA vs AMS: -35% (-1.93  g/m 3 ) Local Hour

Faster hydrolysis more consistent with observations 11 Increasing the hydrolysis rate increases the magnitude of modeled LO-OOA

Faster hydrolysis more consistent with observations Faster hydrolysis improves the speciation of LO-OOA 12 Increasing the hydrolysis rate increases the magnitude of modeled LO-OOA

Faster hydrolysis more consistent with observations Faster hydrolysis improves the speciation of LO-OOA 13 Increasing the hydrolysis rate increases the magnitude of modeled LO-OOA Faster hydrolysis improves the magnitude of gas-phase alkyl nitrates (AN)

25% NO x emission reduction leads to 9% OA reduction 14  g/m 3

Conclusions Gas-phase mechanisms should couple with aerosol-phase mechanisms to provide a realistic depiction of monoterpene+NO 3 chemistry (allows for removal of NO x from the system) Model predictions of ANs and LO-OOA are more consistent with observations when particle-phase hydrolysis is relatively fast (3 hours vs 30 hours) Updates described here (fast hydrolysis) will be available in v5.1 saprc07tic aero6i NO x emission reductions in the Southeast are expected to reduce SOA 15

Office of Research and Development National Exposure Research Laboratory, United States Environmental Protection Agency

Acknowledgements The authors thank Kristen Foley, Jon Pleim, Rohit Mathur, Kathleen Fahey, Rob Pinder, Ron Cohen, and Steve Brown for useful discussion. The authors thank CSC for emission processing, Shaojie Song for GEOS-Chem simulations, William Brune for OH observations, Tran Nguyen and Paul Wennberg (NSF grant AGS ) for CIMS data, and William Brown for ceilometer data. The authors also thank the SOAS field team including Ann Marie Carlton. SEARCH is sponsored by Southern Company and EPRI. Georgia Tech was supported by NSF Grant and US EPA STAR RD and R JLF acknowledges EPA STAR PBS acknowledges EPA STAR R This work has been submitted for publication and is currently under review. 17

Updates to CMAQ saprc07tic Base: Xie et al ACP expanded isoprene chemistry available in CMAQ v5.0.2 saprc07 base (Carter 2010 AE) 10 isoprene nitrates (isoprene+NO 3 follows Rollins et al ACP) 1 lumped nitrate for sources other than isoprene Updates in CMAQ v5.1 for saprc07tic_ae6i ONLY: Tracking of monoterpene nitrates (excluding  -pinene) Tracking of isoprene dinitrates Vapor pressure-based partitioning of monoterpene nitrates and isoprene dinitrates Hydrolysis of particle phase organic nitrates with two assumptions: 10% tertiary nitrate (30 hour lifetime) 100% tertiary nitrate (3 hour lifetime) Updates to gas-phase deposition Other minor changes 18