Megan D. Willis

Light-absorbing properties of ambient black carbon and brown carbon from fossil fuel and biomass burning sources

The optical properties of ambient black carbon-containing particles and the composition of their associated coatings were investigated at a downtown site in Toronto, Canada, for 2 weeks in June 2013. The objective was to assess the relationship between black carbon (BC) coating composition/thickness and absorption. The site was influenced by emissions from local vehicular traffic, wildfires in Quebec, and transboundary fossil fuel combustion emissions in the United States. Mass concentrations of BC and associated nonrefractory coatings were measured using a soot particle–aerosol mass spectrometer (SP-AMS), while aerosol absorption and scattering were measured using a photoacoustic soot spectrometer (PASS). Absorption enhancement was investigated both by comparing ambient and thermally denuded PASS absorption data and by relating absorption data to BC mass concentrations measured using the SP-AMS. Minimal absorption enhancement attributable to lensing at 781 nm was observed for BC using both approaches. However, brown carbon was detected when the site was influenced by wildfire emissions originating in Quebec. BC coating to core mass ratios were highest during this period (~7), and while direct absorption by brown carbon resulted in an absorption enhancement at 405 nm (>2.0), no enhancement attributable to lensing at 781 nm was observed. The efficiency of BC coating removal in the denuder decreased substantially when wildfire-related organics were present and may represent an obstacle for future similar studies. These findings indicate that BC absorption enhancement due to lensing is minimal for downtown Toronto, and potentially other urban locations, even when impacted by long-range transport events.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer

Significance A biogeochemical connection between the atmosphere and the ocean is demonstrated whereby a marine source of oxygenated volatile organic compounds is identified. Compounds of this type are involved in the formation of secondary organic aerosol, which remains one of the most poorly understood components of Earth’s climate system due in part to the diverse sources of its volatile organic compound precursors. This is especially the case for marine environments, where there are more oxygenated volatile organic compounds than can be accounted for by known sources. Although it was observed in the summertime Arctic, this connection may be widespread and important to our understanding of secondary organic aerosol in other remote marine environments, with implications for our understanding of global climate. Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Evidence for marine biogenic influence on summertime Arctic aerosol

We present vertically-resolved observations of aerosol composition during pristine summertime Arctic background conditions. The methansulfonic acid (MSA)-to-sulfate ratio peaked near the surface (mean 0.10), indicating a contribution from ocean-derived biogenic sulfur. Similarly, the organic aerosol (OA)-to-sulfate ratio increased towards the surface (mean 2.0). Both MSA-to-sulfate and OA-to-sulfate ratios were significantly correlated with FLEXPART-WRF-predicted airmass residence time over open water, indicating marine influenced OA. External mixing of sea salt aerosol from a larger number fraction of organic, sulfate and amine-containing particles, together with low wind speeds (median 4.7 m s−1), suggests a role for secondary organic aerosol formation. Cloud condensation nuclei concentrations were nearly constant (∼120 cm−3) when the OA fraction was <60% and increased to 350 cm−3 when the organic fraction was larger and residence times over open water were longer. Our observations illustrate the importance of marine-influenced OA under Arctic background conditions, which are likely to change as the Arctic transitions to larger areas of open water.

Size-resolved mixing state of black carbon in the Canadian high Arctic and implications for simulated direct radiative effect

Transport of anthropogenic aerosol into the Arctic in the spring months has the potential to affect regional climate; however, modeling estimates of the aerosol direct radiative effect (DRE) are sensitive to uncertainties in the mixing state of black carbon (BC). A common approach in previous modeling studies is to assume an entirely external mixture (all primarily 15 scattering species are in separate particles from BC) or internal mixture (all primarily scattering species are mixed in the same particles as BC). To provide constraints on the size-resolved mixing state of BC, we use airborne Single Particle Soot Photometer (SP2) and Ultra-High Sensitivity Aerosol Spectrometer (UHSAS) measurements from the Alfred Wegener Institute (AWI) POLAR6 flights from the NETCARE/PAMARCMIP2015 campaign to estimate coating thickness as a function of refractory BC (rBC) core diameter as well as the fraction of particles containing rBC in the springtime Canadian 20 high Arctic. For rBC core diameters in the range of 140 to 220 nm, we find average coating thicknesses of approximately 45 to 40 nm, respectively, resulting in ratios of total particle diameter to rBC core diameters ranging from 1.6 to 1.4. For total particle diameters ranging from 175 to 730 nm, rBC-containing particle number fractions range from 16 to 3%, respectively. We combine the observed mixing-state constraints with simulated size-resolved aerosol mass and number distributions from GEOS-Chem-TOMAS to estimate the DRE with observed bounds on mixing state as opposed to assuming an entirely 25 external or internal mixture. We find that the pan-Arctic average springtime DRE ranges from -1.65 W m to -1.34 W m when assuming entirely externally or internally mixed BC. Using the observed mixing-state constraints, we find the DRE is 0.05 W m and 0.19 W m less negative than the external mixing-state assumption when constraining by coating thickness of the mixed particles and by BC-containing particle number fraction, respectively. The difference between these methods is due to an underestimation of BC mass fraction in the springtime Arctic in GEOS-Chem-TOMAS compared to POLAR6 30 observations. Measurements of mixing state provide important constraints for model estimates of DRE. Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2018-171 Manuscript under review for journal Atmos. Chem. Phys. Discussion started: 19 February 2018 c

Aircraft measurements of High Arctic springtime aerosol show evidence for vertically varying sources, transport and composition

The sources, chemical transformations and removal mechanisms of aerosol transported to the Arctic are key factors that control Arctic aerosol-climate interactions. Our understanding of sources and processes is limited by a lack of vertically resolved observations in remote Arctic regions. We present vertically resolved observations of trace gases and aerosol composition in High Arctic springtime, made largely north of 80◦N, during the NETCARE campaign. Trace gas gradients observed on these flights defined the polar dome as north of 66 – 68.5◦N and below potential temperatures of 283.5 – 287.5 K (Bozem et al., 5 2018). In the polar dome, we observe evidence for vertically varying source regions and chemical processing. These vertical changes in sources and chemistry lead to systematic variation in aerosol composition as a function of potential temperature. We show evidence for sources of aerosol with higher organic aerosol (OA), ammonium (NH4) and refractory black carbon (rBC) content in the upper polar dome. Based on FLEXPART-ECMWF calculations, air masses sampled at all levels inside the polar dome (i.e., potential temperature < 280.5 K, altitude < ∼3.5 km) subsided during transport over transport times of at 10 least 10 days. Air masses at the lowest potential temperatures, in the lower polar dome, had spent long times (>10 days) in the Arctic, while air masses in the upper polar dome had entered the Arctic more recently. These differences in transport history were closely related to aerosol composition. In the lower polar dome, the measured sub-micron aerosol mass was dominated by sulphate (mean 74%), with lesser contributions from rBC (1%), NH4 (4%) and OA (20%). At higher altitudes and warmer potential temperatures, OA, NH4 and rBC contributed 42%, 8% and 2% of aerosol mass, respectively. A qualitative indication 15 for the presence of sea salt showed that sodium chloride contributed to sub-micron aerosol in the lower polar dome, but was not detectable in the upper polar dome. Our observations suggest that long-term, surface-based measurements underestimate the contribution of OA, rBC and NH4 to aerosol transported to the Arctic troposphere in spring. 1 Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2018-628 Manuscript under review for journal Atmos. Chem. Phys. Discussion started: 24 August 2018 c

Modelling Regional Air Quality in the Canadian Arctic: Simulation of an Arctic Summer Field Campaign

Model simulations of an Arctic summer field campaign were carried out. The model results were compared with observational data from both ground-based monitoring and in situ measurements on-board multiple mobile platforms. The model was able to well capture regional sources and transport affecting the Arctic air quality. It is shown that the study area was impacted by North American (NA) regional biomass burning emissions. The model-observation comparison also corroborates previous findings on possible roles of marine-biogenic sources in aerosol production in the Arctic MBL during summertime.