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Wildfire impacts on air quality and climate are expected to be exacerbated by climate change with the most pronounced impacts in the boreal biome. Despite the large geographic coverage, there is limited information on boreal forest wildfire emissions, particularly for organic compounds, which are critical inputs for air quality model predictions of downwind impacts. In this study, airborne measurements of 193 compounds from 15 instruments, including 173 non-methane organics compounds (NMOG), were used to provide the most detailed characterization, to date, of boreal forest wildfire emissions. Highly speciated measurements showed a large diversity of chemical classes highlighting the complexity of emissions. Using measurements of the total NMOG carbon (NMOGT), the ΣNMOG was found to be 50 % ± 3 % to 53 % ± 3 % of NMOGT, of which, the intermediate- and semi-volatile organic compounds (I/SVOCs) were estimated to account for 7 % to 10 %. These estimates of I/SVOC emission factors expand the volatility range of NMOG typically reported. Despite extensive speciation, a substantial portion of NMOGT remained unidentified (47 % ± 15 % to 50 % ± 15 %), with expected contributions from more highly-functionalized VOCs and I/SVOCs. The emission factors derived in this study improve wildfire chemical speciation profiles and are especially relevant for air quality modelling of boreal forest wildfires. These aircraft-derived emission estimates were further linked with those derived from satellite observations demonstrating their combined value in assessing variability in modelled emissions. These results contribute to the verification and improvement of models that are essential for reliable predictions of near-source and downwind pollution resulting from boreal forest wildfires.

Cyclic volatile methyl siloxanes (cVMSs), which can volatilize into the atmosphere, are active ingredients in widely used consumer products, thus attracting much attention due to their potential environmental risks. While in the atmosphere the cVMSs undergo oxidation, yielding both gaseous and particulate products. The aerosol yields and compositions from the OH oxidation of four cVMSs (D3–D6) were determined under low- and high-NOx conditions in an oxidation flow reactor. The aerosol yields increased progressively from D3 to D6, consistent with the volatilities and molecule weights of these cVMSs. NOx can restrict the formation of secondary organic aerosols (SOAs), leading to lower SOA yields under high-NOx conditions than under low-NOx conditions, with a yield decrease between 0.05–0.30 depending on the cVMSs. Ammonium sulfate seeds exhibited minor impacts on SOA yields under low-NOx conditions but significantly increased the SOA yields in the oxidation of D3–D5 at short photochemical ages under high-NOx conditions. The mass spectra of the SOAs showed a dependence of its chemical compositions on OH exposure. At high exposures equivalent to photochemical ages of >4 d in the atmosphere, D4–D6 SOAs mainly consisted of CxHy and CxHyOzSin under low-NOx conditions, whereas they primarily contained NmOz, CxHy, CxHyO1, CxHyO>1 and CxHyOzSin under high-NOx conditions. The potential contributions of cVMSs to SOA formation in the atmosphere were evaluated using the reported cVMSs annual production and the yield obtained in the present study. A global cVMS-derived (D4–D6) SOA source strength is estimated to be 0.01 Tg yr−1, distributed over major urban centers.

Oil sands are a prominent unconventional source of petroleum. Total organic carbon measurements via an aircraft campaign (Spring-Summer 2018) revealed emissions above Canadian oil sands exceeding reported values by 1900-6300%. The “missing” compounds were predominantly intermediate- and semi-volatile organic compounds, which are prolific precursors to secondary organic aerosol formation. Here we use a novel combination of aircraft-based measurements (including total carbon emissions measurements) and offline analytical instrumentation to characterize the mixtures of organic carbon and their volatility distributions above oil sands facilities. These airborne, real-time observations are supplemented by laboratory experiments identifying substantial, unintended emissions from waste management practices, emphasizing the importance of accurate facility-wide emissions monitoring and total carbon measurements to detect potentially vast missing emissions across sources.Detailed chemical speciation confirms these observations near both surface mining and in-situ facilities were oil sands-derived, with facility-wide emissions around 1% of extracted petroleum—a comparable loss rate to natural gas extraction. Total emissions, spanning extraction through waste processing, were equivalent to total Canadian anthropogenic emissions from all sources. These results demonstrate that the full air quality and environmental impacts of oil sands operations cannot be captured without complete coverage of a wider volatility range of emissions.

Measurement-based estimates of greenhouse gas (GHG) emissions from complex industrial operations are challenging to obtain, but serve as an important, independent check on inventory-reported emissions. Such top–down estimates, while important for oil and gas (O&G) emissions globally, are particularly relevant for Canadian oil sands (OS) operations, which represent the largest O&G contributor to national GHG emissions. We present a multifaceted top–down approach for estimating CO2 emissions that combines aircraft-measured CO2/NOx emission ratios (ERs) with inventory and satellite-derived NOx emissions from Ozone Monitoring Instrument (OMI) and TROPOspheric Ozone Monitoring Instrument (TROPOMI) and apply it to the Athabasca Oil Sands Region (AOSR) in Alberta, Canada. Historical CO2 emissions were reconstructed for the surface mining region, and average top–down estimates were found to be >65% higher than facility-reported, bottom–up estimates from 2005 to 2020. Higher top–down vs. bottom–up emissions estimates were also consistently obtained for individual surface mining and in situ extraction facilities, which represent a growing category of energy-intensive OS operations. Although the magnitudes of the measured discrepancies vary between facilities, they combine such that the observed reporting gap for total AOSR emissions is ≥(31 ± 8) Mt for each of the last 3 years (2018–2020). This potential underestimation is large and broadly highlights the importance of continued review and refinement of bottom–up estimation methodologies and inventories. The ER method herein offers a powerful approach for upscaling measured facility-level or regional fossil fuel CO2 emissions by taking advantage of satellite remote sensing observations.

Organic aerosols are a major component of particulate matter but have a complex and uncertain effect on climate and health.

Commercial chemicals are used extensively across urban centres worldwide

This review is part of a series synthesizing peer-reviewed literature from the past decade on environmental monitoring in the oil sands region (OSR) of northeastern Alberta. It focuses on atmospheric emissions, air quality, and deposition in and downwind of the OSR. Most published monitoring and research activities were concentrated in the surface-mineable region in the Athabasca OSR. Substantial progress has been made in understanding oil sands (OS)-related emission sources using multiple approaches: airborne measurements, satellite measurements, source emission testing, deterministic modeling, and source apportionment modeling. These approaches generally yield consistent results, indicating OS-related sources are regional contributors to nearly all air pollutants. Most pollutants exhibit enhanced air concentrations within ~20 km of surface-mining activities, with some enhanced >100 km downwind. Some pollutants (e.g., sulfur dioxide, nitrogen oxides) undergo transformations as they are transported through the atmosphere. Deposition rates of OS-related substances primarily emitted as fugitive dust are enhanced within ~30 km of surface-mining activities, whereas gaseous and fine particulate emissions have a more diffuse deposition enhancement pattern extending hundreds of kilometers downwind. In general, air quality guidelines are not exceeded, although these single-pollutant thresholds are not comprehensive indicators of air quality. Odor events have occurred in communities near OS industrial activities, although it can be difficult to attribute events to specific pollutants or sources. Nitrogen, sulfur, polycyclic aromatic compounds (PACs), and base cations from OS sources occur in the environment, but explicit and deleterious responses of organisms to these pollutants are not as apparent across all study environments; details of biological monitoring are discussed further in other papers in this special series. However, modeling of critical load exceedances suggests that, at continued emission levels, ecological change may occur in future. Knowledge gaps and recommendations for future work to address these gaps are also presented. Integr Environ Assess Manag 2021;00:1-28. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Liquid crystal monomers (LCMs) are synthetic chemicals widely used in liquid crystal displays such as televisions and smartphones and have recently been detected in indoor dust. Despite extensive u...

Tailings ponds in the oil sands (OS) region in Alberta, Canada, have been associated with fugitive emissions of volatile organic compounds (VOCs) and other pollutants to the atmosphere. However, the contribution of tailings ponds to the total fugitive emissions of VOCs from OS operations remains uncertain. To address this knowledge gap, a field study was conducted in the summer of 2017 at Suncor's Pond 2/3 to estimate emissions of a suite of pollutants including 68 VOCs using a combination of micrometeorological methods and measurements from a flux tower. The results indicate that in 2017, Pond 2/3 was an emission source of 3322 ± 727 tons of VOCs including alkanes, aromatics, and oxygenated and sulfur-containing organics. While the total VOC emissions were approximately a factor of 2 higher than those reported by Suncor, the individual VOC species emissions varied by up to a factor of 12. A chemical mass balance (CMB) receptor model was used to estimate the contribution of the tailings pond to VOC pollution events in a nearby First Nations and Metis community in Fort McKay. CMB results indicate that Suncor Pond 2/3 contributed up to 57% to the total mass of VOCs measured at Fort McKay, reinforcing the importance of accurate VOC emission estimation methods for tailings ponds.

Reactive organic compounds play a central role in the formation of ozone and secondary organic aerosols. The ability to accurately predict their fate, in part, relies upon quantitative knowledge of the chemical and physical parameters associated with the total organic carbon (TOC), which includes both precursors and oxidation products that evolve in the atmosphere over short to long time scales. However, such knowledge, obtained via limited carbon closure experiments, has not been attained for complex anthropogenic emissions. Here we present the first comprehensive characterization of TOC in the atmospheric oxidation of organic vapors from light and heavy oil mixtures associated with oil sand operations. Despite the complexity of the investigated oil mixtures, we are able to achieve carbon closure (83-116%) within the uncertainties (±20%), with the degree of the closure being dependent upon the vapor composition and NOx levels. In contrast to biogenic precursors (e.g., α-pinene), the photochemical time scale required for a largely complete oxidation and evolution of chemical parameters is very long for the petrochemical vapors (i.e., ∼7-10 days vs ∼1 day), likely due to the lower initial precursor reactivity. This suggests that petrochemical emissions and their impacts are likely to extend further spatially than biogenic emissions, and retain more of their complex composition and reactivity for many days. The results of this work provide key parameters to regional models for further improving the representation of the chemical evolution of petrochemical emissions.

Inhalation of airborne engineered nanoparticles (ENPs) is an important pathway for population exposure. While there have been numerous studies of the health impacts of pristine ENPs, the impacts of...

Oil sands (OS) are an important type of heavy oil deposit, for which operations in Alberta, Canada, were recently found to be a large source of secondary organic aerosol (SOA). However, SOA formati...

Oil-sands (OS) operations in Alberta, Canada, are a large source of secondary organic aerosol (SOA). However, the SOA formation process from OS-related precursors remains poorly understood. In this work, a newly developed oxidation flow reactor (OFR), the Environment and Climate Change Canada OFR (ECCC-OFR), was characterized and used to study the yields and composition of SOA formed from OH oxidation of α-pinene, selected alkanes, and the vapors evolved from five OS-related samples (OS ore, naphtha, tailings pond water, bitumen, and dilbit). The derived SOA yields from α-pinene and selected alkanes using the ECCC-OFR were in good agreement with those of traditional smog chamber experiments but significantly higher than those of other OFR studies under similar conditions. The results also suggest that gas-phase reactions leading to fragmentation (i.e., C–C bond cleavage) have a relatively small impact on the SOA yields in the ECCC-OFR at high photochemical ages, in contrast to other previously reported OFR results. Translating the impact of fragmentation reactions in the ECCC-OFR to ambient atmospheric conditions reduces its impact on SOA formation even further. These results highlight the importance of careful evaluation of OFR data, particularly when using such data to provide empirical factors for the fragmentation process in models. Application of the ECCC-OFR to OS-related precursor mixtures demonstrated that the SOA yields from OS ore and bitumen vapors (maximum of ∼0.6–0.7) are significantly higher than those from the vapors from solvent use (naphtha), effluent from OS processing (tailings pond water), and from the solvent diluted bitumen (dilbit; maximum of ∼0.2–0.3), likely due to the volatility of each precursor mixture. A comparison of the yields and elemental ratios (H∕C and O∕C) of the SOA from the OS-related precursors to those of linear and cyclic alkane precursors of similar carbon numbers suggests that cyclic alkanes play an important role in the SOA formation in the OS. The analysis further indicates that the majority of the SOA formed downwind of OS facilities is derived from open-pit mining operations (i.e., OS ore evaporative emissions) rather than from higher-volatility precursors from solvent use during processing and/or tailings management. The current results have implications for improving the regional modeling of SOA from OS sources, for the potential mitigation of OS precursor emissions responsible for observed SOA downwind of OS operations, and for the understanding of petrochemical- and alkane-derived SOA in general.

The oil and gas (O&G) sector represents a large source of greenhouse gas (GHG) emissions globally. However, estimates of O&G emissions rely upon bottom-up approaches, and are rarely evaluated through atmospheric measurements. Here, we use aircraft measurements over the Canadian oil sands (OS) to derive the first top-down, measurement-based determination of the their annual CO2 emissions and intensities. The results indicate that CO2 emission intensities for OS facilities are 13–123% larger than those estimated using publically available data. This leads to 64% higher annual GHG emissions from surface mining operations, and 30% higher overall OS GHG emissions (17 Mt) compared to that reported by industry, despite emissions reporting which uses the most up to date and recommended bottom-up approaches. Given the similarity in bottom-up reporting methods across the entire O&G sector, these results suggest that O&G CO2 emissions inventory data may be more uncertain than previously considered., Evaluating GHG emissions reported to inventories for the oil and gas (O&G) sector is important for countries with resource-based economies. Here the authors provide a top-down assessment of GHG emissions from the Canadian oil sands and find previous inventory reports underestimate emissions, by as much as 64% for surface mining facilities and 30% for the entire oil sands compared with their assessment.

Commercial chemicals are used extensively across global urban centers, posing a potential exposure risk to 4.2 billion people, which accounts for 55% of the global population. Harmful chemicals are often assessed and regulated based on their environmental persistence, bioaccumulation, and toxic properties, under international and national initiatives such as the Stockholm Convention. However, current regulatory frameworks largely rely upon knowledge of the properties of the parent chemicals, with minimal consideration given to their atmospheric transformation products. This is mainly due to a significant lack of experimental data, as identifying transformation products in complex mixtures of airborne chemicals is an immense analytical challenge,hence making a comprehensive and reliable risk assessment for harmful chemicals currently unachievable. Here, we develop a novel framework, combining laboratory and field experiments, non-target analysis techniques, and in-silico modelling, to identify and assess the hazards of airborne chemicals, which takes into account atmospheric chemical reactions. By applying this framework to organophosphate flame retardants, as representative chemicals of emerging concern, we find that their transformation products are globally distributed across 18 megacities, representing a previously unrecognized exposure risk for the world’s urban populations. Furthermore, the transformation products can be up to an order of magnitude more persistent, environmentally mobile, and toxic than the parent chemicals. The results indicate that the overall human and environmental risks associated with flame retardants could be significantly underestimated, while highlighting a strong need to include atmospheric transformations in the development of regulations for all harmful chemicals moving forward.

Smoke from wildfires are a significant source of air pollution, which can adversely impact ecosystems and the air quality in downwind populated areas. With increasing severity of wildfires over the years, these are a significant threat to air quality in densely populated areas. Emissions from wildfires are most commonly estimated by a bottom-up approach, using proxies such fuel type, burn area, and emission factors. Emissions are also commonly derived with a top-down approach, using satellite observed Fire Radiative Power. Furthermore, wildfire emissions can also be estimated directly from satellite-borne measurements.Here, we present advancements and improvements of direct emission estimates of forest fire NOx emissions by using TROPOMI (Tropospheric Monitoring Instrument) high-resolution satellite datasets, including NO2 vertical column densities (VCDs) and information on plume height and aerosol scattering. The effect of smoke aerosols on the sensitivity of TROPOMI to NO2 (via air mass factors) is estimated with recalculated VCDs, and validated with aircraft observations. Different top-down emission estimation methods are tested on synthetic data to determine the accuracy, and the sensitivity to parameters, such as wind fields, satellite sampling, instrument noise, NO2:NOx conversion ratio, species atmosphere lifetime and plume spread. Lastly, the top-down, bottom-up and direct emission estimates of fire emissions are quantitatively compared.

The Athabasca Oil Sands Region (AOSR) in Alberta, Canada is one of the largest sources of extractable oil in the world. To better understand its impact, Environment and Climate Change Canada led two intensive measurement campaigns, in 2013 (August to September) and 2018 (April to July). Each included airborne measurements in which dozens of species were measured using a variety of in situ instruments. In this presentation, a method is described in which these aircraft measurements were examined to find species that were well correlated with NOx (the sum of NO and NO2) in order to derive their annual emissions. The species found to have a good correlation with NOx were black carbon, CO, HCN, HONO, CH4, and SO2. The annual emissions were found by applying individual species to NOx ratios to the satellite-derived NOx emissions from the TROPOspheric Monitoring Instrument (TROPOMI). The emissions derived in this way were compared with emissions reported to the National Pollutant Release Inventory (NPRI), as well as emissions derived from the aircraft measurements using the Top-down Emission Rate Retrieval Algorithm (TERRA). Additionally, Ozone Monitoring Instrument (OMI) NOx emissions were used to estimate historical changes in species emissions over time, between 2005 and 2020.

Forest fires are major contributors of reactive gas- and particle-phase organic compounds to the atmosphere. We used offline high resolution tandem mass spectrometry to perform a molecular-level speciation of evolving gas- and particle-phase compounds sampled via aircraft from a boreal forest fire in Saskatchewan, Canada. We observed diverse multifunctional compounds containing oxygen, nitrogen, and sulfur (CHONS), whose structure, formation, and impacts are understudied. The abundance of particle-phase CHONS species increased with plume age, from 19 % to 40 % of the relative abundance of observed functionalized OA over the first 4 hours of downwind transport. The relative contribution of particle-phase sulfide functional groups increased with age from 4 % to 40 % of observed OA abundance, and were present in up to 75 % of CHONS compounds. The increases in sulfides were accompanied by increases in ring-bound nitrogen, and both increased together with CHONS prevalence. A complex mixture of intermediate- and semi-volatile gas-phase organic sulfur species was emitted from the fire and depleted downwind, representing potential precursors to particle-phase CHONS compounds. These results demonstrate CHONS formation from nitrogen/oxygen-containing biomass burning emissions in the presence of reduced sulfur species, and highlight chemical pathways that may also be relevant in situations with elevated levels of nitrogen and sulfur emissions from residential biomass burning and fossil fuel use (e.g. coal), respectively.

Formic and acetic acid are ubiquitous and abundant in the Earth's atmosphere and are important contributors to cloud water acidity, especially in remote regions. Their global sources are not well understood, as evidenced by the inability of models to reproduce the magnitude of measured mixing ratios, particularly at high northern latitudes. The scarcity of measurements at those latitudes is also a hindrance to understanding these acids and their sources. Here, we present ground-based gas-phase measurements of formic acid (FA) and acetic acid (AA) in the Canadian Arctic collected at 0.5 Hz with a high-resolution chemical ionization time-of-flight mass spectrometer using the iodide reagent ion (iodide HR-ToF-CIMS, Aerodyne). This study was conducted at Alert, Nunavut, in the early summer of 2016. FA and AA mixing ratios for this period show high temporal variability and occasional excursions to very high values (up to 11 and 40 ppbv respectively). High levels of FA and AA were observed under two very different conditions: under overcast, cold conditions during which physical equilibrium partitioning should not favor their emission, and during warm and sunny periods. During the latter, sunny periods, the FA and AA mixing ratios also displayed diurnal cycles in keeping with a photochemical source near the ground. These observations highlight the complexity of the sources of FA and AA, and suggest that current chemical transport model implementations of the sources of FA and AA in the Arctic may be incomplete.

Semivolatile organic compounds (SVOCs) represent a dominant category of secondary organic aerosol precursors that are increasingly included in air quality models. In the present study, an experimental system was developed and applied to a light-duty diesel engine to determine the emission factors of particulate SVOCs (pSVOCs) and nonvolatile particulate matter (PM) components at dilution ratios representative of ambient conditions. The engine was tested under three steady-state operation modes, using ultra-low-sulfur diesel (ULSD), three types of pure biodiesels and their blends with ULSD. For ULSD, the contribution of pSVOCs to total particulate organic matter (POM) mass in the engine exhaust ranged between 21 and 85%. Evaporation of pSVOCs from the diesel particles during dilution led to decreases in the hydrogen to carbon ratio of POM and the PM number emission factor of the particles. Substituting biodiesels for ULSD could increase pSVOCs emissions but brought on large reductions in black carbon (BC) emissions. Among the biodiesels tested, tallow/used cooking oil (UCO) biodiesel showed advantages over soybean and canola biodiesels in terms of both pSVOCs and nonvolatile PM emissions. It is noteworthy that PM properties, such as particle size and BC mass fraction, differed substantially between emissions from conventional diesel and biodiesels.

Ambient volatile organic compounds (VOCs) at a suburban Beijing site were on-line detected using proton transfer reaction-mass spectrometry (PTR-MS) during autumn of 2014, near the location of the Asia-Pacific Economic Cooperation (APEC) summit. During the APEC summit, the Chinese government enacted strict emission control policies. It was found that VOC concentrations only slightly decreased during the first emission control period (EC I), when control policies were performed in Beijing and 5 cities along the Tai-hang Mountains. However, most of the VOCs (10 out of 12 non-biogenic species) significantly decreased (more than 40%) during the second emission control period (EC II), when control policies were carried out in 16 cities including Beijing, Tianjin, 8 cities of Hebei province and 6 cities of Shandong province. Also the ratio of toluene and benzene decreased during EC II, likely because the emission control policies changed the proportions of different anthropogenic sources. Using the positive matrix factorization (PMF) source apportionment method, five factors are analyzed: (1) vehicle + fuel, (2) solvent, (3) biomass burning, (4) secondary, and (5) background + long-lived. Among them, vehicle + fuel, solvent and biomass burning contribute most of the VOCs concentrations (60%–80%) during the polluted periods and are affected most by emission control policies. During EC II, the reductions of vehicle + fuel, solvent, biomass burning and secondary species were all no less than 50%. Overall, when emission control policies were carried out in many North China Plain (NCP) cities (i.e. EC II), the VOC concentrations of suburban Beijing markedly decreased. This indicates the cross-regional joint-control policies have a large influence on reductions of organic gas species. The findings of this study have vital implications for helping formulate effective emission control policies in China and other countries.

Black carbon (BC) emissions from the Canadian oil sand (OS) surface mining facilities in Alberta were investigated using aircraft measurements. BC emission rates were derived with a top-down mass balance approach and were found to be linearly related to the volume of oil sand ore mined at each facility. Two emission factors were determined from the measurements; production-based BC emission factors were in the range of 0.6-1.7 g/tonne mined OS ore, whereas fuel-based BC emission factors were between 95 and 190 mg/kg-fuel, depending upon the facility. The annual BC emission, at 707 ± 117 tonnes/year for the facilities, was determined using the production-based emission factors and annual production data. Although this annual emission is in reasonable agreement with the BC annual emissions reported in the latest version of the Canadian national BC inventory (within 16%), the relative split between off-road diesel and stack sources is significantly different between the measurements and the inventory. This measurement evidence highlights the fact that the stack sources of BC may be overestimated and the off-road diesel sources may be underestimated in the inventory and points to the need for improved BC emission data from diesel sources within facilities.

The environmental risks and health impacts associated with particulate organophosphate flame retardants (OPFRs), which are ubiquitous in the global atmosphere, have not been adequately assessed due to the lack of data on the reaction kinetics, products, and toxicity associated with their atmospheric transformations. Here, the importance of such transformations for OPFRs are explored by investigating the reaction kinetics, degradation chemical mechanisms, and toxicological evolution of two OPFRs (2-ethylhexyl diphenyl phosphate (EHDP) and diphenyl phosphate (DPhP)) coated on (NH4)2SO4 particles upon heterogeneous OH oxidation. The derived reaction rate constants for the heterogeneous loss of EHDP and DPhP are (1.12 ± 0.22) × 10-12 and (2.33 ± 0.14) × 10-12 cm3 molecules-1 s-1, respectively. Using recently developed real-time particle chemical composition measurements, particulate products from heterogeneous photooxidation and the associated degradation mechanisms for particulate OPFRs are reported for the first time. Subsequent cytotoxicity analysis of the unreacted and oxidized OPFR particles indicated that the overall particle cytotoxicity was reduced by up to 94% with heterogeneous photooxidation, likely due to a significantly lower cytotoxicity associated with the oxidized OPFR products relative to the parent OPFRs. The present work not only provides guidance for future field sampling for the detection of transformation products of OPFRs, but also strongly supports the ongoing risk assessment of these emerging chemicals and most critically, their products.

Oil sands (OS) are an important type of heavy oil deposit, for which operations in Alberta, Canada, were recently found to be a large source of secondary organic aerosol (SOA). However, SOA formation from the OS mining, processing, and subsequent tailings, especially in the presence of NO

The current uncertainties in the reactivity and atmospheric persistence of particle-associated chemicals present a challenge for the prediction of long-range transport and deposition of emerging chemicals such as organophosphate flame retardants, which are ubiquitous in the global environment. Here, the OH-initiated heterogeneous oxidation kinetics of organophosphate flame retardants (OPFRs) coated on inert (NH4)2SO4 and redox-active FeSO4 particles were systematically determined as a function of relative humidity (RH). The derived reaction rate constants for the heterogeneous loss of tricresyl phosphate (TCP; kTCP) and tris(2-butoxyethyl) phosphate (TBEP; kTBEP) were in the range of (2.69-3.57) × 10-12 and (3.06-5.55) × 10-12 cm3 molecules-1 s-1, respectively, depending on the RH and coexisting Fe(II) content. The kTCP (coated on (NH4)2SO4) was relatively constant over the investigated RH range while kTBEP was enhanced by up to 19% with increasing RH. For both OPFRs, the presence of Fe(II) enhanced their k by up to 53% over inert (NH4)2SO4. These enhancement effects (RH and Fe(II)) were attributed to fundamental changes in the organic phase state (higher RH lowered particle viscosity) and Fenton-type chemistry which resulted in the formation of reactive oxygen species, respectively. Such findings serve to emphasize the importance of ambient RH, the phase state of particle-bound organics in general, and the presence of coexisting metallic species for an accurate description of the degradation kinetics and aging of particulate OPFRs in models used to evaluate their atmospheric persistence.

Oil sands (OS) operations in Alberta, Canada are a large source of secondary organic aerosol (SOA). However, the SOA formation process from OS-related precursors remains poorly understood. In this work, a newly developed oxidation flow reactor (OFR), the Environment and Climate Change Canada OFR (ECCC-OFR), was characterized and used to study the yields and composition of SOA formed from OH oxidation of α-pinene, selected alkanes, and the vapors evolved from five OS-related samples (OS ore, naphtha, tailings pond water, bitumen, and dilbit). The derived SOA yields from α-pinene and selected alkanes using the ECCC-OFR were in good agreement with those of traditional smog chamber experiments, but significantly higher than those of other OFR studies under similar conditions. The results also suggest that gas-phase reactions leading to fragmentation (i.e., C-C bond cleavage) have a relatively small impact on the SOA yields in the ECCC-OFR at high photochemical ages, in contrast to other previously reported OFR results. Translating the impact of fragmentation reactions in the ECCC-OFR to ambient atmospheric conditions reduces its impact on SOA formation even further. These results highlight the importance of careful evaluation of OFR data, particularly when using such data to provide empirical factors for the fragmentation process in models. Application of the ECCC-OFR to OS-related precursor mixtures, demonstrated that the SOA yields from OS ore and bitumen vapors (maximum of ~ 0.6–0.7) are significantly higher than those from the vapors from solvent use (naphtha), effluent from OS processing (tailing pond water) and from the solvent diluted bitumen (dilbit) (maximum of ~ 0.2–0.3), likely due to the volatility of each precursor mixture. A comparison of the yields and elemental ratios (H / C and O / C) of the SOA from the OS-related precursors to those of linear and cyclic alkane precursors of similar carbon numbers suggests that cyclic alkanes play an important role in the SOA formation in the OS. The analysis further indicates that the majority of the SOA formed downwind of OS facilities is derived from open-pit mining operations (i.e., OS ore evaporative emissions), rather than from higher volatility precursors from solvent use during processing and/or tailing management. The current results have implications for improving the regional modeling of SOA from OS sources, for the potential mitigation of OS precursor emissions responsible for observed SOA downwind of OS operations, and for the understanding of petrochemical and alkane derived SOA in general.

Secondary organic aerosol (SOA) plays a pivotal role in visibility and radiative forcing, both of which are intrinsically linked to the refractive index (RI). While previous studies have focused on the RI of SOA from traditional formation processes, the effect of multiphase reactions on the RI has not been considered. Here, we investigate the effects of multiphase processes on the RI and light-extinction of m-xylene-derived SOA, a common type of anthropogenic SOA. We find that multiphase reactions in the presence of liquid water lead to the formation of oligomers from intermediate products such as glyoxal and methylglyoxal, resulting in a large enhancement in the RI and light-scattering of this SOA. These reactions will result in increases in light-scattering efficiency and direct radiative forcing of approximately 20%-90%. These findings improve our understanding of SOA optical properties and have significant implications for evaluating the impacts of SOA on the rapid formation of regional haze, global radiative balance, and climate change.

Secondary organic aerosol (SOA) formation from photooxidation of α-pinene has been investigated in a photochemical reaction chamber under varied inorganic seed particle acidity levels at moderate relative humidity. The effect of particle acidity on SOA yield and chemical composition was examined under high- and low-NOx conditions. The SOA yield (4.2–7.6 %) increased nearly linearly with the increase in particle acidity under high-NOx conditions. In contrast, the SOA yield (28.6–36.3 %) was substantially higher under low-NOx conditions, but its dependency on particle acidity was insignificant. A relatively strong increase in SOA yield (up to 220 %) was observed in the first hour of α-pinene photooxidation under high-NOx conditions, suggesting that SOA formation was more effective for early α-pinene oxidation products in the presence of fresh acidic particles. The SOA yield decreased gradually with the increase in organic mass in the initial stage (approximately 0–1 h) under high-NOx conditions, which is likely due to the inaccessibility to the acidity over time with the coating of α-pinene SOA, assuming a slow particle-phase diffusion of organic molecules into the inorganic seeds. The formation of later-generation SOA was enhanced by particle acidity even under low-NOx conditions when introducing acidic seed particles after α-pinene photooxidation, suggesting a different acidity effect exists for α-pinene SOA derived from later oxidation stages. This effect could be important in the atmosphere under conditions where α-pinene oxidation products in the gas-phase originating in forested areas (with low NOx and SOx) are transported to regions abundant in acidic aerosols such as power plant plumes or urban regions. The fraction of oxygen-containing organic fragments (CxHyO1+ 33–35 % and CxHyO2+ 16–17 %) in the total organics and the O ∕ C ratio (0.52–0.56) of α-pinene SOA were lower under high-NOx conditions than those under low-NOx conditions (39–40, 17–19, and 0.61–0.64 %), suggesting that α-pinene SOA was less oxygenated in the studied high-NOx conditions. The fraction of nitrogen-containing organic fragments (CxHyNz+ and CxHyOzNp+) in the total organics was enhanced with the increases in particle acidity under high-NOx conditions, indicating that organic nitrates may be formed heterogeneously through a mechanism catalyzed by particle acidity or that acidic conditions facilitate the partitioning of gas-phase organic nitrates into particle phase. The results of this study suggest that inorganic acidity has a significant role to play in determining various organic aerosol chemical properties such as mass yields, oxidation state, and organic nitrate content. The acidity effect being further dependent on the timescale of SOA formation is also an important parameter in the modeling of SOA.

Dimethyl sulfide (DMS) plays a major role in the global sulfur cycle. In addition, its atmospheric oxidation products contribute to the formation and growth of atmospheric aerosol particles, thereby influencing cloud condensation nuclei (CCN) populations and thus cloud formation. The pristine summertime Arctic atmosphere is strongly influenced by DMS. However, atmospheric DMS mixing ratios have only rarely been measured in the summertime Arctic. During July–August, 2014, we conducted the first high time resolution (10 Hz) DMS mixing ratio measurements for the eastern Canadian Archipelago and Baffin Bay as one component of the Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments (NETCARE). DMS mixing ratios ranged from below the detection limit of 4 to 1155 pptv (median 186 pptv) during the 21-day shipboard campaign. A transfer velocity parameterization from the literature coupled with coincident atmospheric and seawater DMS measurements yielded air–sea DMS flux estimates ranging from 0.02 to 12 µmol m−2 d−1. Air-mass trajectory analysis using FLEXPART-WRF and sensitivity simulations with the GEOS-Chem chemical transport model indicated that local sources (Lancaster Sound and Baffin Bay) were the dominant contributors to the DMS measured along the 21-day ship track, with episodic transport from the Hudson Bay System. After adjusting GEOS-Chem oceanic DMS values in the region to match measurements, GEOS-Chem reproduced the major features of the measured time series but was biased low overall (2–1006 pptv, median 72 pptv), although within the range of uncertainty of the seawater DMS source. However, during some 1–2 day periods the model underpredicted the measurements by more than an order of magnitude. Sensitivity tests indicated that non-marine sources (lakes, biomass burning, melt ponds, and coastal tundra) could make additional episodic contributions to atmospheric DMS in the study region, although local marine sources of DMS dominated. Our results highlight the need for both atmospheric and seawater DMS data sets with greater spatial and temporal resolution, combined with further investigation of non-marine DMS sources for the Arctic.

Substantial biogenic secondary organic aerosol (BSOA) formation was investigated in a coniferous forest mountain region in Whistler, British Columbia. A largely biogenic aerosol growth episode was observed, providing a unique opportunity to investigate BSOA formation chemistry in a forested environment with limited influence from anthropogenic emissions. Positive matrix factorization of aerosol mass spectrometry (AMS) measurement identified two types of BSOA (BSOA-1 and BSOA-2), which were primarily generated by gas-phase oxidation of monoterpenes and perhaps sesquiterpenes. The temporal variations of BSOA-1 and BSOA-2 can be explained by gas–particle partitioning in response to ambient temperature and the relative importance of different oxidation mechanisms between day and night. While BSOA-1 arises from gas-phase ozonolysis and nitrate radical chemistry at night, BSOA-2 is likely less volatile than BSOA-1 and consists of products formed via gas-phase oxidation by OH radical and ozone during the day. Organic nitrates produced through nitrate radical chemistry can account for 22–33 % of BSOA-1 mass at night. The mass spectra of BSOA-1 and BSOA-2 have higher values of the mass fraction of m/z 91 (f91) compared to the background organic aerosol. Using f91 to evaluate BSOA formation pathways in this unpolluted, forested region, heterogeneous oxidation of BSOA-1 is a minor production pathway of BSOA-2.

Hydrogen cyanide (HCN) is considered a marker for biomass burning emissions and is a component of vehicle exhaust. Despite its potential health impacts, vehicular HCN emissions estimates and their contribution to regional budgets are highly uncertain. In the current study, Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-ToF-MS) was used to measure HCN emission factors from the exhaust of individual diesel, biodiesel and gasoline vehicles. Laboratory emissions data as a function of fuel type and driving mode were combined with ambient measurement data and model predictions. The results indicate that gasoline vehicles have the highest emissions of HCN (relative to diesel fuel) and that biodiesel fuel has the potential to significantly reduce HCN emissions even at realistic 5% blend levels. The data further demonstrate that gasoline direct injection (GDI) engines emit more HCN than their port fuel injection (PFI) counterparts, suggesting that the expected full transition of vehicle fleets to GDI will increase HCN emissions. Ambient measurements of HCN in a traffic dominated area of Toronto, Canada were strongly correlated to vehicle emission markers and consistent with regional air quality model predictions of ambient air HCN, indicating that vehicle emissions of HCN are the dominant source of exposure in urban areas. The results further indicate that additional work is required to quantify HCN emissions from the modern vehicle fleet, particularly in light of continuously changing engine, fuel and after-treatment technologies.

Particle phase organic carbon (OC), elemental carbon (EC) and particle phase semi-volatile organic carbon were measured simultaneously at two distances downwind of a highway using an integrated organic gas and particle sampler. This method reduces sampling artifacts associated with OC measurement. On average, artifact-corrected OC (referred to as OC T ) was 2.4 μg/m 3 and the positive and negative artifacts were significant at 0.8 and 1.0 μg/m 3 respectively. Close to the highway negative artifacts are potentially dominant over positive artifacts indicating that traditional integrated filter-based sampling for OC and fine particles (PM 2.5 ) may be biased low. Decreases in OC T between the near and far site ranged from 25 to 44% while the decreases observed for EC, which reflects the impact of dispersion, were larger at 42–84%. The nature of the OC T changed between sites becoming less volatile and having a greater content of pyrolized organic carbon. Collectively, these results suggest that secondary organic aerosol (SOA) formed downwind of the highway from vehicle-related emissions and was detectable within the 15 min transit time between the highway and the far site. These results highlight the need for improvements in understanding the processes influencing organic aerosols in locations directly impacted by motor vehicle emissions in order to realistically predict PM 2.5 using air quality models.

Motivated by the need to predict how the Arctic atmosphere will change in a warming world, this article summarizes recent advances made by the research consortium NETCARE (Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments) that contribute to our fundamental understanding of Arctic aerosol particles as they relate to climate forcing. The overall goal of NETCARE research has been to use an interdisciplinary approach encompassing extensive field observations and a range of chemical transport, earth system, and biogeochemical models. Several major findings and advances have emerged from NETCARE since its formation in 2013 . (1) Unexpectedly high summertime dimethyl sulfide (DMS) levels were identified in ocean water and the overlying atmosphere in the Canadian Arctic Archipelago (CAA). Furthermore, melt ponds, which are widely prevalent, were identified as an important DMS source. (2) Evidence was found of widespread particle nucleation and growth in the marine boundary layer in the CAA in the summertime. DMS-oxidation-driven nucleation is facilitated by the presence of atmospheric ammonia arising from sea bird colony emissions, and potentially also from coastal regions, tundra, and biomass burning. Via accumulation of secondary organic material (SOA), a significant fraction of the new particles grow to sizes that are active in cloud droplet formation. Although the gaseous precursors to Arctic marine SOA remain poorly defined, the measured levels of common continental SOA precursors (isoprene and monoterpenes) were low, whereas elevated mixing ratios of oxygenated volatile organic compounds were inferred to arise via processes involving the sea surface microlayer. (3) The variability in the vertical distribution of black carbon (BC) under both springtime Arctic haze and more pristine summertime aerosol conditions was observed. Measured particle size distributions and mixing states were used to constrain, for the first time, calculations of aerosol–climate interactions under Arctic conditions. Aircraft- and ground-based measurements were used to better establish the BC source regions that supply the Arctic via long-range transport mechanisms. (4) Measurements of ice nucleating particles (INPs) in the Arctic indicate that a major source of these particles is mineral dust, likely derived from local sources in the summer and long-range transport in the spring. In addition, INPs are abundant in the sea surface microlayer in the Arctic, and possibly play a role in ice nucleation in the atmosphere when mineral dust concentrations are low. (5) Amongst multiple aerosol components, BC was observed to have the smallest effective deposition velocities to high Arctic snow.