Atmospheric black carbon (BC) warms Earth's climate, and its reduction has been targeted for near-term climate change mitigation. Models that include forcing by BC assume internal mixing with non-BC aerosol components that enhance BC absorption, often by a factor of ~2; such model estimates have yet to be clearly validated through atmospheric observations. Here, direct in situ measurements of BC absorption enhancements (E(abs)) and mixing state are reported for two California regions. The observed E(abs) is small-6% on average at 532 nm-and increases weakly with photochemical aging. The E(abs) is less than predicted from observationally constrained theoretical calculations, suggesting that many climate models may overestimate warming by BC. These ambient observations stand in contrast to laboratory measurements that show substantial E(abs) for BC are possible.

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TROPOspheric Monitoring Instrument (TROPOMI), on‐board the Sentinel‐5 Precurser satellite, is a nadir‐viewing spectrometer measuring reflected sunlight in the ultraviolet, visible, near‐infrared, and shortwave infrared. From these spectra several important air quality and climate‐related atmospheric constituents are retrieved, including nitrogen dioxide (NO2) at unprecedented spatial resolution from a satellite platform. We present the first retrievals of TROPOMI NO2 over the Canadian Oil Sands, contrasting them with observations from the Ozone Monitoring Instrument satellite instrument, and demonstrate TROPOMI's ability to resolve individual plumes and highlight its potential for deriving emissions from individual mining facilities. Further, the first TROPOMI NO2 validation is presented, consisting of aircraft and surface in situ NO2 observations, and ground‐based remote‐sensing measurements between March and May 2018. Our comparisons show that the TROPOMI NO2 vertical column densities are highly correlated with the aircraft and surface in situ NO2 observations, and the ground‐based remote‐sensing measurements with a low bias (15–30 %); this bias can be reduced by improved air mass factors.

Worldwide heavy oil and bitumen deposits amount to 9 trillion barrels of oil distributed in over 280 basins around the world, with Canada home to oil sands deposits of 1.7 trillion barrels. The global development of this resource and the increase in oil production from oil sands has caused environmental concerns over the presence of toxic compounds in nearby ecosystems and acid deposition. The contribution of oil sands exploration to secondary organic aerosol formation, an important component of atmospheric particulate matter that affects air quality and climate, remains poorly understood. Here we use data from airborne measurements over the Canadian oil sands, laboratory experiments and a box-model study to provide a quantitative assessment of the magnitude of secondary organic aerosol production from oil sands emissions. We find that the evaporation and atmospheric oxidation of low-volatility organic vapours from the mined oil sands material is directly responsible for the majority of the observed secondary organic aerosol mass. The resultant production rates of 45-84 tonnes per day make the oil sands one of the largest sources of anthropogenic secondary organic aerosols in North America. Heavy oil and bitumen account for over ten per cent of global oil production today, and this figure continues to grow. Our findings suggest that the production of the more viscous crude oils could be a large source of secondary organic aerosols in many production and refining regions worldwide, and that such production should be considered when assessing the environmental impacts of current and planned bitumen and heavy oil extraction projects globally.

S1 Solutions from positive matrix factorisa-1 tion 2 For this study, a four factor solution was determined to best represent the 3 measured aerosol. A two factor solution separates the Ship Emissions factor 4 from the ambient background aerosol, while a three factor solution includes 5 the Organic factor. It is only with four factors that the Marine Biogenic 6 factor is separated from the Continental factor. Additional factors either 7 identify instrumental noise, or split the existing factors. Figure S1 shows 8 the decrease in Q/Q exp as additional factors are included, where Q exp is 9 the expected Q. We see that including a 5 th factor decreases Q/Q exp by 10 identifying instrumental noise, while additional factors only serve to capture 11 episodic events, often coinciding with ship emissions. Even though Q/Q exp 12 decreased slightly from 3.36 for four factors down to 3.06 for 10 factors, 13 including more factors did not contribute additional information about the 14 measured aerosol. As such, the four factor solution was deemed to give the 15 most information about the measured ambient aerosol. 16 The robustness of the solution can be explored by either varying the initial 17 seed, which changes the set of pseudorandom values used for the initial point 18 (Paatero, 1997), or by using bootstrapping analysis, in which the rows of X 19 are randomly sampled and PMF is executed on the new dataset (as described 20 by Reff et al., 2007). Both of these methods were used and the four factor 21 solution at fPeak =-0.75 was found to be robust: 100 values for the initial 22 seed parameter in the PMF2 program resulted in 90 of the cases giving the 23 solution presented here, while 100 iterations of the bootstrapping analysis 24 S1

Large-scale oil production from oil sands deposits in Alberta, Canada has raised concerns about environmental impacts, such as the magnitude of air pollution emissions. This paper reports compound emission rates (E) for 69-89 nonbiogenic volatile organic compounds (VOCs) for each of four surface mining facilities, determined with a top-down approach using aircraft measurements in the summer of 2013. The aggregate emission rate (aE) of the nonbiogenic VOCs ranged from 50 ± 14 to 70 ± 22 t/d depending on the facility. In comparison, equivalent VOC emission rates reported to the Canadian National Pollutant Release Inventory (NPRI) using accepted estimation methods were lower than the aE values by factors of 2.0 ± 0.6, 3.1 ± 1.1, 4.5 ± 1.5, and 4.1 ± 1.6 for the four facilities, indicating underestimation in the reported VOC emissions. For 11 of the combined 93 VOC species reported by all four facilities, the reported emission rate and E were similar; but for the other 82 species, the reported emission rate was lower than E. The median ratio of E to that reported for all species by a facility ranged from 4.5 to 375 depending on the facility. Moreover, between 9 and 53 VOCs, for which there are existing reporting requirements to the NPRI, were not included in the facility emission reports. The comparisons between the emission reports and measurementbased emission rates indicate that improvements to VOC emission estimation methods would enhance the accuracy and completeness of emission estimates and their applicability to environmental impact assessments of oil sands developments.volatile organic compounds | emissions | emission inventory validation | oil sands | aircraft measurements

Abstract. Top-down approaches to measure total integrated emissions provide verification of bottom-up, temporally resolved, inventory-based estimations. Aircraft-based measurements of air pollutants from sources in the Canadian oil sands were made in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring during a summer intensive field campaign between 13 August and 7 September 2013. The measurements contribute to knowledge needed in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring. This paper describes the top-down emission rate retrieval algorithm (TERRA) to determine facility emissions of pollutants, using SO 2 and CH 4 as examples, based on the aircraft measurements. In this algorithm, the flight path around a facility at multiple heights is mapped to a two-dimensional vertical screen surrounding the facility. The total transport of SO 2 and CH 4 through this screen is calculated using aircraft wind measurements, and facility emissions are then calculated based on the divergence theorem with estimations of box-top losses, horizontal and vertical turbulent fluxes, surface deposition, and apparent losses due to air densification and chemical reaction. Example calculations for two separate flights are presented. During an upset condition of SO 2 emissions on one day, these calculations are within 5 % of the industryreported, bottom-up measurements. During a return to normal operating conditions, the SO 2 emissions are within 11 % of industry-reported, bottom-up measurements. CH 4 emissions calculated with the algorithm are relatively constant within the range of uncertainties. Uncertainty of the emission rates is estimated as less than 30 %, which is primarily due to the unknown SO 2 and CH 4 mixing ratios near the surface below the lowest flight level.

[1] Reliable characterization of particles freshly emitted from the ocean surface requires a sampling method that is able to isolate those particles and prevent them from interacting with ambient gases and particles. Here we report measurements of particles directly emitted from the ocean using a newly developed in situ particle generator (Sea Sweep). The Sea Sweep was deployed alongside R/V Atlantis off the coast of California during May of 2010. Bubbles were generated 0.75 m below the ocean surface with stainless steel frits and swept into a hood/vacuum hose to feed a suite of aerosol instrumentation on board the ship. The number size distribution of the directly emitted, nascent particles had a dominant mode at 55-60 nm (dry diameter) and secondary modes at 30-40 nm and 200-300 nm. The nascent aerosol was not volatile at 230 C and was not enriched in SO 4 = , Ca ++ , K + , or Mg ++ above that found in surface seawater. The organic component of the nascent aerosol (7% of the dry submicrometer mass) volatilized at a temperature between 230 and 600 C. The submicrometer organic aerosol characterized by mass spectrometry was dominated by non-oxygenated hydrocarbons. The nascent aerosol at 50, 100, and 145 nm dry diameter behaved hygroscopically like an internal mixture of sea salt with a small organic component. The CCN/CN activation ratio for 60 nm Sea Sweep particles was near 1 for all supersaturations of 0.3 and higher indicating that all of the particles took up water and grew to cloud drop size. The nascent organic aerosol mass fraction did not increase in regions of higher surface seawater chlorophyll but did show a positive correlation with seawater dimethylsulfide (DMS).