Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site

Abstract

Abstract. A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 > 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black carbon (BC ~ 0.2 μg m−3). Particle-phase sulfate is fairly correlated (r2 ~ 0.3) with both methacrylic acid epoxide (MAE)/hydroxymethyl-methyl-α-lactone (HMML)- (henceforth called methacrolein (MACR)-derived SOA tracers) and IEPOX-derived SOA tracers, and more strongly correlated (r2 ~ 0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the MACR-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2 = 0.38) and nitrate (r2 = 0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2 ~ 0.5 and ~ 0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC as well as aerosol viscosity and morphology becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

Simulating Aqueous-Phase Isoprene-Epoxydiol (IEPOX) Secondary Organic Aerosol Production During the 2013 Southern Oxidant and Aerosol Study (SOAS)

“…21 However, ground-based studies in the eastern US suggest weak or no correlation between IEPOX SOA and aerosol pH or liquid water content (LWC), but a positive correlation with sulfate. 9,11 Additionally, a preliminary modeling study employing simpleGAMMA found good correlation (r 2 ∼ 0.6) between estimated IEPOX SOA and measurements made during the 2013 Southern Oxidant Aerosol Study (SOAS) campaign. 9 This study aims to investigate the formation of two IEPOX SOA tracers, IEPOXOS and tetrols, using CMAQ and simpleGAMMA algorithms, and evaluate the model response to perturbations that replicate atmospheric conditions.…”

“…9,11 Additionally, a preliminary modeling study employing simpleGAMMA found good correlation (r 2 ∼ 0.6) between estimated IEPOX SOA and measurements made during the 2013 Southern Oxidant Aerosol Study (SOAS) campaign. 9 This study aims to investigate the formation of two IEPOX SOA tracers, IEPOXOS and tetrols, using CMAQ and simpleGAMMA algorithms, and evaluate the model response to perturbations that replicate atmospheric conditions. Predictions from these two different algorithms are compared with measurement results from the 2013 SOAS campaign.…”

“…IEPOX-derived organosulfates (IEPOXOS) and tetrols, which have been quantified in laboratory experiments, 17,18 have been shown to contribute up to half of all known IEPOXderived aerosol-phase species in the southeastern U.S. 8,9 The accepted formation pathway for IEPOX SOA is through acidcatalyzed ring-opening reactions of isoprene epoxides in concert with nucleophilic addition in aqueous particles. 18−20 An airborne study over the southeastern U.S. found a strong dependency between IEPOXOS and acidic sulfate aerosol.…”

“…Among isoprene-derived SOA tracers, 2-methyltetrols (tetrols) and their sulfate ester derivatives (organosulfates) contribute ∼33% and ∼34% of IEPOX-OA, respectively, at the Look Rock (LRK), Tennessee site. 9 Inclusion of biogenic and anthropogenic SOA precursors and mechanisms in the Community Multiscale Air Quality (CMAQ) model improves the temporal correlation between predicted and semiempirical secondary organic carbon (OC). 12 Addition of the acid-catalyzed reactive uptake mechanism of IEPOX into CMAQ further improves predictions of tetrols against field measurements.…”

“…7 On average, isoprene-derived SOA tracers account for up to 20% of total OA observed in the southeastern U.S. (SE US), and compounds derived from isoprene epoxydiol (IEPOX) chemical pathways can account for >95% of isoprene SOA. 8,9 IEPOX-OA, a positive matrix factor linked to IEPOX-derived SOA (IEPOX SOA) tracers, comprises one-third of ambient organic aerosol mass in urban and rural areas in the SE US, 9−11 suggesting a regional source. Among isoprene-derived SOA tracers, 2-methyltetrols (tetrols) and their sulfate ester derivatives (organosulfates) contribute ∼33% and ∼34% of IEPOX-OA, respectively, at the Look Rock (LRK), Tennessee site.…”