Field intercomparison of continuous ambient FRM and FEM NO2 instruments in the Athabasca Oil Sands Region, Alberta, Canada and the potential impact on ambient regulatory compliance.

The Canadian Federal Government promulgated new and lower NO2 Ambient Air Quality Standards (CAAQS) that went into effect in 2020 with additional decreases scheduled for 2025. The new hourly and annual NO2 CAAQS are 60 and 17 ppb, respectively, and the 2025 hourly and annual CAAQS are 42 and 12 ppb, respectively. The province of Alberta has also promulgated Ambient Air Quality Objectives (AAAQO) for NO2 currently set to 159 and 24 ppb on an hourly and annual basis, respectively. The Wood Buffalo Environmental Association (WBEA) in northeastern Alberta, Canada monitors NO2 at 21 community and industrial sites throughout the Athabasca Oil Sands Region (AOSR), for regulatory compliance using Thermo-Environmental (TEI) Model 42i Federal Reference Method (FRM) designated NO-NO2-NOx analyzers. The 42i measures NO directly via NO-O3 chemiluminescence, and NOx following the reduction of oxidized nitrogen to NO by a heated internal molybdenum converter. The difference between the NOx and NO channels is reported as NO2. This study presents the results of a three-year (2018-2021) WBEA comparison of four continuous NO2 analyzers: TEI 42i FRM; the API Model T500U cavity attenuated phase shift (CAPS) Federal Equivalent Method (FEM); a total reactive odd nitrogen analyzer (TEI Model 42i-Y); and a TEI 42i equipped with an external photolytic converter. The study showed that NO2 data from all analyzers were highly correlated and in general agreement, with r2 values (vs. the CAPS) ranging from 0.990-0.997 and slopes ranging from 0.933-0.992. Mean NO2 concentrations over the study period ranged from 7.2-7.5 ppb. Differences between the TEI 42i, TEI 42i-Y, and PhoNO, relative to the CAPS were all positive and highly significant (p < 0.0001), based upon nonparametric tests. The potential impact from the selection of different FRM/FEM measurement methods on current and future Canadian 2025 regulatory compliance in the region is evaluated.Implications: The study objective was to compare/evaluate different regulatory NO2 measurement techniques from a regional monitoring authority in a routine network operational context. Relatively small NO2 differences resulted in significant differences with respect to regulatory compliance triggers, particularly hourly standards based on daily extreme value statistics (e.g., 99th percentiles). For example, mean hourly NO2 △ differences ranged from 0.02-0.26 ppb over the study period but resulted in 2-3 ppb differences in the 3-year hourly CAAQS metrics. These differences could affect regulatory CAAQS and LARP compliance (management level) at monitoring sites observed during 2019 annual and 2020 hourly LARP trigger exceedances.

Atmospheric Dry and Wet Deposition of Total Phosphorus to the Great Lakes.

Quantifying atmospheric loadings of total phosphorus (TP) to freshwater environments is essential to improve understanding of its fate and transport, and to mitigate the effects of excessive levels in freshwater ecosystems. To date, atmospheric deposition of TP in the U.S. is poorly characterized due to the lack of long-term deposition observations. Here, we integrate several historical datasets to develop an estimate of dry and wet deposition to the Great Lakes region. For dry deposition, we use TP concentrations in fine particulate matter (PM2.5) samples from fourteen land-based IMPROVE sites (2013-2020) upwind of the Great Lakes to provide new fine particle phosphorus dry deposition estimates. For wet deposition, we use TP concentrations in wet-only precipitation samples collected at eleven land-based sites (2001-2009) in the Great Lakes region. For both wet and dry deposition, a seasonal cycle is evident with higher concentrations in warmer and wetter months when compared to colder months. Additionally, there is an increasing gradient from north to south in wet deposition, likely driven by both higher precipitation and increased emissions near southern sites. Despite different sampling time periods, these updated observations can provide further constraints on the TP loadings to each of the five Great Lakes. We estimate annual deposition of TP to Lakes Superior, Michigan, Huron, Erie and Ontario at 526, 702, 495, 212, and 185 MTA per year, which is lower than prior estimates for Lakes Superior, Erie and Ontario, comparable for Lake Huron, and about two times greater for Lake Michigan. When considering only the contribution of fine particulate PM to the dry deposition, wet deposition dominated over dry at all lakes except for Lake Huron. However, prior global estimates suggest greater contributions from larger particles (PM10 and PM100), yet observations to validate these estimates over the Great Lakes are not available. Our findings indicate that dry deposition of a range of particle sizes are needed to constrain the total atmospheric deposition of TP over the Great Lakes.

Summary of PM2.5 measurement artifacts associated with the Teledyne T640 PM Mass Monitor under controlled chamber experimental conditions using polydisperse ammonium sulfate aerosols and biomass smoke.

Particulate matter (PM) is a major primary pollutant emitted during wildland fires that has the potential to pose significant health risks to individuals/communities who live and work in areas impacted by smoke events. Limiting exposure is the principle measure available to mitigate health impacts of smoke and therefore the accurate determination of ambient PM concentrations during wildland fire events is critical to protecting public health. However, monitoring air pollutants in smoke impacted environments has proven challenging in that measurement interferences or sampling conditions can result in both positive and negative artifacts. The EPA has performed research on methods for the measurement of PM2.5 in a series of laboratory-based studies including evaluation in smoke. This manuscript will summarize the results of the laboratory-based evaluation of federal equivalent method (FEM) monitors for PM2.5 with particular attention being given to the Teledyne-API Model T640 PM Mass monitor, as compared to the filter-based federal reference method (FRM). The T640 is an optical-based PM monitor and has been gaining wide use by state and local agencies in monitoring for PM2.5 U.S. National Ambient Air Quality Standards (NAAQS) attainment. At present, the T640 (includes both T640 and T640×) comprises ~44% of the PM2.5 FEM monitors in U.S. regulatory monitoring networks. In addition, the T640 has increasingly been employed for the higher time resolution comparison/evaluation of low-cost PM sensors including during smoke impacted events. Results from controlled non-smoke laboratory studies using generated ammonium sulfate aerosols demonstrated a generally negative T640 measurement artifact that was significantly related to the PM2.5 concentration and particle size distribution. Results from biomass burning chamber studies demonstrated positive and negative artifacts significantly associated with PM2.5 concentration and optical wavelength-dependent absorption properties of the smoke aerosol.Implications: The results detailed in this paper will provide state and local air monitoring agencies with the tools and knowledge to address PM2.5 measurement challenges in areas frequently impacted by wildland fire smoke. The observed large positive and negative artifacts in the T640 PM mass determination have the potential to result in false exceedances of the PM2.5 NAAQS or in the disqualification of monitoring data through an exceptional event designation. In addition, the observed artifacts in smoke impacted air will have a detrimental effect on providing reliable public information when wildfires occur and also in identifying reference measurements for small sensor evaluation studies. Other PM2.5 FEMs such as the BAM-1022 perform better in smoke and are comparable to the filter-based FRM. Care must be taken in choosing high time resolution FEM monitors that will be operated at smoke impacted sites. Accurate methods, such as the FRM and BAM-1022 will reduce the burden of developing and reviewing exceptional event request packages, data loss/disqualification, and provide states with tools to adequately evaluate public exposure risks and provide accurate public health messaging during wildfire/smoke events.

An evaluation of empirical and statistically based smoke plume injection height parametrisations used within air quality models.

Air quality models are used to assess the impact of smoke from wildland fires, both prescribed and natural, on ambient air quality and human health. However, the accuracy of these models is limited by uncertainties in the parametrisation of smoke plume injection height (PIH) and its vertical distribution. We compared PIH estimates from the plume rise method (Briggs) in the Community Multiscale Air Quality (CMAQ) modelling system with observations from the 2013 California Rim Fire and 2017 prescribed burns in Kansas. We also examined PIHs estimated using alternative plume rise algorithms, model grid resolutions and temporal burn profiles. For the Rim Fire, the Briggs method performed as well or better than the alternatives evaluated (mean bias of less than ±5-20% and root mean square error lower than 1000 m compared with the alternatives). PIH estimates for the Kansas prescribed burns improved when the burn window was reduced from the standard default of 12 h to 3 h. This analysis suggests that meteorological inputs, temporal allocation and heat release are the primary drivers for accurately modelling PIH.

Evaluation of Cairpol and Aeroqual Air Sensors in Biomass Burning Plumes.

Cairpol and Aeroqual air quality sensors measuring CO, CO2, NO2, and other species were tested in fresh biomass burning plumes in field and laboratory environments. We evaluated sensors by comparing 1-minute sensor measurements to collocated reference instrument measurements. Sensors were evaluated based on the coefficient of determination (r 2) between the sensor and reference measurements, by the accuracy, collocated precision, root mean square error (RMSE), and other metrics. In general, CO and CO2 sensors performed well (in terms of accuracy and r 2 values) compared to NO2 sensors. Cairpol CO and NO2 sensors had better sensor-versus-sensor agreement (e.g., collocated precision) than Aeroqual CO and NO2 sensors of the same species. Tests of other sensors (e.g., NH3, H2S, VOC, NMHC) provided more inconsistent results and need further study. Aeroqual NO2 sensors had an apparent O3 interference that was not observed in the Cairpol NO2 sensors. Although the sensor accuracy lags that of reference-level monitors, with location-specific calibrations they have the potential to provide useful data about community air quality and personal exposure to smoke impacts.

Fuel layer specific pollutant emission factors for fire prone forest ecosystems of the western U.S. and Canada.

Wildland fires are a major source of gases and aerosols, and the production, dispersion, and transformation of fire emissions have significant ambient air quality impacts and climate interactions. The increase in wildfire area burned and severity across the United States and Canada in recent decades has led to increased interest in expanding the use of prescribed fires as a forest management tool. While the primary goal of prescribed fire use is to limit the loss of life and property and ecosystem damage by constraining the growth and severity of future wildfires, a potential additional benefit of prescribed fire - reduction in the adverse impacts of smoke production and greenhouse gas (GHG) emissions - has recently gained the interest of land management agencies and policy makers in the United States and other nations. The evaluation of prescribed fire/wildfire scenarios and the potential mitigation of adverse impacts on air quality and GHGs requires fuel layer specific pollutant emission factors (EFs) for fire prone forest ecosystems. Our study addresses this need with laboratory experiments measuring EFs for carbon dioxide (CO2), carbon monoxide (CO), methane (CH4), ethyne (C2H2), formaldehyde (H2CO), formic acid (CH2O2), hydrogen cyanide (HCN), fine particulate matter (PM2.5), nitric oxide (NO), nitrogen dioxide (NO2), sulfur dioxide (SO2), and total reduced sulfur (TRS) for the burning of individual fuel components from three forest ecosystems which account for a large share of wildfire burned area and emissions in the western United States and Canada - Douglas fir, ponderosa pine, and black spruce/jack pine.

Associations of Air Pollution and Pediatric Asthma in Cleveland, Ohio.

Air pollution has been associated with poor health outcomes and continues to be a risk factor for respiratory health in children. While higher particulate matter (PM) levels are associated with increased frequency of symptoms, lower lung function, and increase airway inflammation from asthma, the precise composition of the particles that are more highly associated with poor health outcomes or healthcare utilization are not fully elucidated. PM is measured quantifiably by current air pollution monitoring systems. To better determine sources of PM and speciation of such sources, a particulate matter (PM) source apportionment study, the Cleveland Multiple Air Pollutant Study (CMAPS), was conducted in Cleveland, Ohio, in 2009-2010, which allowed more refined assessment of associations with health outcomes. This article presents an evaluation of short-term (daily) and long-term associations between motor vehicle and industrial air pollution components and pediatric asthma emergency department (ED) visits by evaluating two sets of air quality data with healthcare utilization for pediatric asthma. Exposure estimates were developed using land use regression models for long-term exposures for nitrogen dioxide (NO2) and coarse (i.e., with aerodynamic diameters between 2.5 and 10 µm) particulate matter (PM) and the US EPA Positive Matrix Factorization receptor model for short-term exposures to fine (<2.5 µm) and coarse PM components. Exposure metrics from these two approaches were used in asthma ED visit prevalence and time series analyses to investigate seasonal-averaged short- and long-term impacts of both motor vehicles and industry emissions. Increased pediatric asthma ED visits were found for LUR coarse PM and NO2 estimates, which were primarily contributed by motor vehicles. Consistent, statistically significant associations with pediatric asthma visits were observed, with short-term exposures to components of fine and coarse iron PM associated with steel production. Our study is the first to combine spatial and time series analysis of ED visits for asthma using the same periods and shows that PM related to motor vehicle emissions and iron/steel production are associated with increased pediatric asthma visits.

Comparison of ozone measurement methods in biomass burning smoke: an evaluation under field and laboratory conditions.

In recent years wildland fires in the United States have had significant impacts on local and regional air quality and negative human health outcomes. Although the primary health concerns from wildland fires come from fine particulate matter (PM2.5), large increases in ozone (O3) have been observed downwind of wildland fire plumes (DeBell et al., 2004; Bytnerowicz et al., 2010; Preisler et al., 2010; Jaffe et al., 2012; Bytnerowicz et al., 2013; Jaffe et al., 2013; Lu et al., 2016; Lindaas et al., 2017; McClure and Jaffe, 2018; Liu et al., 2018; Baylon et al., 2018; Buysse et al., 2019). Conditions generated in and around wildland fire plumes, including the presence of interfering chemical species, can make the accurate measurement of O3 concentrations using the ultraviolet (UV) photometric method challenging if not impossible. UV photometric method instruments are prone to interferences by volatile organic compounds (VOCs) that are present at high concentrations in wildland fire smoke. Four different O3 measurement methodologies were deployed in a mobile sampling platform downwind of active prescribed grassland fire lines in Kansas and Oregon and during controlled chamber burns at the United States Forest Service, Rocky Mountain Research Station Fire Sciences Laboratory in Missoula, Montana. We demonstrate that the Federal Reference Method (FRM) nitric oxide (NO) chemiluminescence monitors and Federal Equivalent Method (FEM) gas-phase (NO) chemical scrubber UV photometric O3 monitors are relatively interference-free, even in near-field combustion plumes. In contrast, FEM UV photometric O3 monitors using solid-phase catalytic scrubbers show positive artifacts that are positively correlated with carbon monoxide (CO) and total gas-phase hydrocarbon (THC), two indicator species of biomass burning. Of the two catalytic scrubber UV photometric methods evaluated, the instruments that included a Nafion® tube dryer in the sample introduction system had artifacts an order of magnitude smaller than the instrument with no humidity correction. We hypothesize that Nafion®-permeating VOCs (such as aromatic hydrocarbons) could be a significant source of interference for catalytic scrubber UV photometric O3 monitors and that the inclusion of a Nafion® tube dryer assists with the mitigation of these interferences. The chemiluminescence FRM method is highly recommended for accurate measurements of O3 in wildland fire plume studies and at regulatory ambient monitoring sites frequently impacted by wildland fire smoke.

The U.S. EPA wildland fire sensor challenge: Performance and evaluation of solver submitted multi-pollutant sensor systems.

Wildland fires can emit substantial amounts of air pollution that may pose a risk to those in proximity (e.g., first responders, nearby residents) as well as downwind populations. Quickly deploying air pollution measurement capabilities in response to incidents has been limited to date by the cost, complexity of implementation, and measurement accuracy. Emerging technologies including miniaturized direct-reading sensors, compact microprocessors, and wireless data communications provide new opportunities to detect air pollution in real time. The U.S. Environmental Protection Agency (EPA) partnered with other U.S. federal agencies (CDC, NASA, NPS, NOAA, USFS) to sponsor the Wildland Fire Sensor Challenge. EPA and partnering organizations share the desire to advance wildland fire air measurement technology to be easier to deploy, suitable to use for high concentration events, and durable to withstand difficult field conditions, with the ability to report high time resolution data continuously and wirelessly. The Wildland Fire Sensor Challenge encouraged innovation worldwide to develop sensor prototypes capable of measuring fine particulate matter (PM2.5), carbon monoxide (CO), carbon dioxide (CO2), and ozone (O3) during wildfire episodes. The importance of using federal reference method (FRM) versus federal equivalent method (FEM) instruments to evaluate performance in biomass smoke is discussed. Ten solvers from three countries submitted sensor systems for evaluation as part of the challenge. The sensor evaluation results including sensor accuracy, precision, linearity, and operability are presented and discussed, and three challenge winners are announced. Raw solver submitted PM2.5 sensor accuracies of the winners ranged from ~22 to 32%, while smoke specific EPA regression calibrations improved the accuracies to ~75-83% demonstrating the potential of these systems in providing reasonable accuracies over conditions that are typical during wildland fire events.

Evaluation of small form factor, filter-based PM2.5 samplers for temporary non-regulatory monitoring during wildland fire smoke events.

Wildland fire activity and associated emission of particulate matter air pollution is increasing in the United States over the last two decades due primarily to a combination of increased temperature, drought, and historically high forest fuel loading. The regulatory monitoring networks in the Unites States are mostly concentrated in larger population centers where anthropogenic air pollution sources are concentrated. Smaller population centers in areas more likely to be impacted by wildland fire smoke in many instances lack adequate observational air quality data. Several commercially available small form factor filter-based PM2.5 samplers (SFFFS) were evaluated under typical ambient and simulated near-to mid-field wildland fire smoke conditions to evaluate their accuracy for use in temporary deployments during prescribed and wildfire events. The performance of all the SFFFS tested versus the designated federal reference methods (FRM) was acceptable in determining PM2.5 concentration in both ambient (2.7-14.0 µg m-3) and chamber smoke environments (24.6-3044.6 µg m-3) with accuracies ranging from ~92 to 98%. However, only the ARA Instruments model N-FRM Sampler was found to provide PM2.5 mass measurement accuracies that meet FRM guideline performance specifications under both typical ambient (97.3 ± 1.9%) and simulated wildland fire conditions (98.2 ± 1.4%).

Ambient concentrations and total deposition of inorganic sulfur, inorganic nitrogen and base cations in the Athabasca Oil Sands Region.

Trace gas, particulate matter and deposition data collected in the Athabasca Oil Sands Region (AOSR) from 2000 to 2017 were evaluated as part of a broad scientific programmatic review. Results showed significant spatial patterns and temporal trends across the region. Concentrations of reactive gases were highest near the center of surface oil sands production operations and decreased towards the edges of the monitoring domain by factors of 8, 20, 4 and 3 for SO2, NO2, HNO3 and NH3, respectively. 18 of 30 sites showed statistically significant (p < 0.05) negative trends in SO2 concentrations suggesting an ~40% decrease since 2000. In contrast, only 2 of 30 sites showed statistically significant temporal trends (1 positive, 1 negative) for NO2. NH3 data showed (i) intermittent wildfire impacts, and (ii) high seasonality, with low concentrations during winter and significantly higher values during the summer. PM10 measurements were more limited, but also showed significant spatio-temporal variability. Comparison of PM10 and PM2.5 data showed that >80% of SO42- was in the PM2.5 fraction, while > 60% of Ca2+, Mg2+, Na+ and Cl- were in the PM10-2.5 fraction. Ion balances of both PM10 and PM2.5 contained cation excesses at near-field oil sand sites, but PM2.5 samples at forest health sites >20 km from surface production locations contained anion excesses. Monthly average concentrations of PM10 ions showed peak Ca2+ during March-April to November, but peak SO42-, NH4+ and NO3- from November-March. Deposition estimates showed rapid declines as a function of distance to oil sand operations. Estimated total N and total S deposition to forest health monitoring sites ranged from 2.0 to 5.7 kg ha-1 a-1 and 2.1-14.0 kg ha-1 a-1, respectively. Potential acid input (PAI) ranged from -0.46 to 0.79 keq ha-1 a-1 and was mostly 0.1-0.2 keq ha-1 a-1 throughout the domain, except for two clusters of sites near oil sand operations.

Use of an epiphytic lichen and a novel geostatistical approach to evaluate spatial and temporal changes in atmospheric deposition in the Athabasca Oil Sands Region, Alberta, Canada.

Temporal and spatial atmospheric deposition trends of elements to the boreal forest surrounding bitumen production operations in the Athabasca Oil Sands Region (AOSR), Alberta, Canada were investigated as part of a long-term lichen bioindicator study. The study focused on eight elements (sulfur, nitrogen, aluminum, calcium, iron, nickel, strontium, vanadium) that were previously identified as tracers for the major oil sand production sources. Samples of the in situ epiphytic lichen Hypogymnia physodes were collected in 2002, 2004, 2008, 2011, 2014, and 2017 within a ~150 km radius from the center of surface oil sand production operations in the AOSR. Site-specific time series analysis conducted at eight jack pine upland sites that were repeatedly sampled generally showed significant trends of increasing lichen concentrations for fugitive dust linked elements, particularly at near-field (<25 km from a major oil sands production operation) sample locations. Multiple regional scale geostatistical models were developed and evaluated to characterize broad-scale changes in atmospheric deposition based on changes in H. physodes elemental concentrations between 2008 and 2014. Empirical Bayesian kriging and cokriging lichen element concentrations with oil sands mining, bitumen upgrading, coke materials handling, and limestone quarry/crushing influence variables produced spatial interpolation estimates with the lowest validation errors. Gridded zonal mean lichen element concentrations were calculated for the two comprehensive sampling years (2008, 2014) and evaluated for spatial and temporal change. Lichen sulfur concentrations significantly increased in every grid cell within the domain with the largest increases (44-88%) in the central valley in close proximity to the major surface oil sand production operations, while a minor nitrogen concentration decrease (-20%) in a single grid cell was observed. The areal extent of fugitive dust element deposition generally increased with significantly higher deposition to lichens restricted to the outer grids of the enhanced deposition field, reflecting new and expanding surface mining activity.

The role of fuel type and combustion phase on the toxicity of biomass smoke following inhalation exposure in mice.

The characteristics of wildland fire smoke exposures which initiate or exacerbate cardiopulmonary conditions are unclear. We previously reported that, on a mass basis, lung toxicity associated with particulate matter (PM) from flaming smoke aspirated into mouse lungs is greater than smoldering PM. In this study, we developed a computer-controlled inhalation system which can precisely control complex biomass smoke emissions from different combustion conditions. This system was used to examine the toxicity of inhaled biomass smoke from peat, eucalyptus, and oak fuels generated under smoldering and flaming phases with emissions set to the same approximate concentration of carbon monoxide (CO) for each exposure (60-110 ppm), resulting in PM levels of ~ 4 mg/m3 for flaming and ~ 40 mg/m3 for smoldering conditions. Mice were exposed by inhalation 1 h/day for 2 days, and assessed for lung toxicity at 4 and 24 h after the final exposure. Peat (flaming and smoldering) and eucalyptus (smoldering) smoke elicited significant inflammation (neutrophil influx) in mouse lungs at 4 h with the peat (flaming) smoke causing even greater lung inflammation at 24-h post-exposure. A significant alteration in ventilatory timing was also observed in mice exposed to the peat (flaming) and eucalyptus (flaming and smoldering) smoke immediately after each day of exposure. No responses were seen for exposures to similar concentrations of flaming or smoldering oak smoke. The lung toxicity potencies (neutrophil influx per PM mass) agreed well between the inhalation and previously reported aspiration studies, demonstrating that although flaming smoke contains much less PM mass than smoldering smoke, it is more toxic on a mass basis than smoldering smoke exposure, and that fuel type is also a controlling factor.

Source apportionment of an epiphytic lichen biomonitor to elucidate the sources and spatial distribution of polycyclic aromatic hydrocarbons in the Athabasca Oil Sands Region, Alberta, Canada.

The sources and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) atmospheric deposition in the boreal forests surrounding bitumen production operations in the Athabasca Oil Sands Region (AOSR), Alberta, Canada were investigated as part of a 2014 passive in-situ bioindicator source apportionment study. Epiphytic lichen species Hypogymnia physodes samples (n = 127) were collected within a 150 km radius of the main surface oil sand production operations and analyzed for total sulfur, total nitrogen, forty-three elements, twenty-two PAHs, ten groups of C1-C2-alkyl PAHs and dibenzothiophenes (polycyclic aromatic compounds; PACs), five C1- and C2-alkyldibenzothiophenes, and retene. The ΣPAH + PAC in H. physodes ranged from 54 to 2778 ng g-1 with a median concentration of 317 ng g-1. Source apportionment modeling found an eight-factor solution that explained 99% of the measured ΣPAH + PAC lichen concentrations from four anthropogenic oil sands production sources (Petroleum Coke, Haul Road Dust, Stack Emissions, Raw Oil Sand), two local/regional sources (Biomass Combustion, Mobile Source), and two lichen biogeochemical factors. Petroleum Coke and Raw Oil Sand dust were identified as the major contributing sources of ΣPAH + PAC in the AOSR. These two sources accounted for 63% (43.2 µg g-1) of ΣPAH + PAC deposition to the entire study domain. Of this overall 43.2 µg g-1 contribution, approximately 90% (39.9 µg g-1) ΣPAH + PAC was deposited within 25 km of the closest oil sand production facility. Regional sources (Biomass Combustion and Mobile Sources) accounted for 19% of ΣPAH + PAC deposition to the entire study domain, of which 46% was deposited near-field to oil sand production operations. Source identification was improved over a prior lichen-based study in the AOSR through incorporation of PAH and PAC analytes in addition to inorganic analytes.

Using Pb isotope ratios of particulate matter and epiphytic lichens from the Athabasca Oil Sands Region in Alberta, Canada to quantify local, regional, and global Pb source contributions.

Ambient air particulate matter (PM) was collected at the Wood Buffalo Environmental Association Bertha Ganter Fort McKay monitoring station in the Athabasca Oil Sand Region (AOSR) in Alberta, Canada from February 2010 to July 2011 as part of an air quality source assessment study. Daily 24-hour duration fine (PM2.5) and coarse (PM10-2.5) PM was collected using a sequential dichotomous sampler. 100 pairs of PM2.5 and PM10-2.5 were selected for lead (Pb) concentration and isotope analysis. Pb isotope and concentration results from 250 epiphytic lichen samples collected as far as 160 km from surface mining operations in 2008, 2011, and 2014 were analyzed to examine longer term spatial variations in Pb source contributions. A key finding was recognition of thorogenic 208Pb from eastern Asia in the springtime in the PM2.5 in 2010 and 2011. 206Pb/207Pb and 208Pb/207Pb isotope ratios were used in a three-component mixing model to quantify local, regional, and global Pb sources in the PM and lichen data sets. 47 ±â€¯3% of the Pb in the PM2.5 at AMS-1 was attributed to sources from eastern Asia. Combined results from PM10-2.5 and PM2.5 indicate PM2.5 Pb contributions from eastern Asia (34%) exceed local AOSR sources of PM2.5 Pb (20%), western Canada sources of PM2.5 Pb (19%), and PM10-2.5 Pb from fugitive dust including oil sands (14%), tailings (10%), and haul roads (3%). The lichen analysis indicates regional sources contribute 46% of the Pb, local sources 32%, and global sources 22% over the 2008-2014 timeframe. Local sources dominate atmospheric Pb deposition to lichens at near field sites (0-30 km from mining operations) whereas regional Pb sources are prevalent at distal sites (30-160 km). The Pb isotope methodology successfully quantified trans-Pacific transport of Pb to the AOSR superimposed over the aerosol footprint of the world's largest concentration of bitumen mining and upgrading facilities.

Source apportionment of ambient fine and coarse particulate matter polycyclic aromatic hydrocarbons at the Bertha Ganter-Fort McKay community site in the Oil Sands Region of Alberta, Canada.

A comprehensive filter-based particulate matter polycyclic aromatic hydrocarbon (PAH) source apportionment study was conducted at the Wood Buffalo Environmental Association Bertha Ganter-Fort McKay (BGFM) community monitoring station from 2014 to 2015 to quantify ambient concentrations and identify major sources. The BGFM station is located in close proximity to several surface oil sands production facilities and was previously found to be impacted by their air emissions. 24-hour integrated PM2.5 and PM10-2.5 samples were collected on a 1-in-3-day schedule yielding 108 complete organic/inorganic filter sets for source apportionment modeling. During the study period PM2.5 averaged 8.6 ±â€¯11.8 µg m-3 (mean ±â€¯standard deviation), and PM10-2.5 averaged 8.5 ±â€¯9.5 µg m-3. Wind regression analysis indicated that the oil sands production facilities were significant sources of PM2.5 mass and black carbon (BC), and that wildland fires were a significant source of the highest PM2.5 (>10 µg m-3) and BC events. A six-factor positive matrix factorization (PMF) model solution explained 95% of the measured PM2.5 and 78% of the measured ΣPAH. Five sources significantly contributed to PM2.5 including: Biomass Combustion (3.57 µg m-3; 40%); Fugitive Dust (1.86 µg m-3; 28%); Upgrader Stack Emissions (1.44 µg m-3; 21%); Petrogenic PAH (1.20 µg m-3; 18%); and Transported Aerosol (0.43 µg m-3 and 6%). However, the analysis indicated that only the pyrogenic PAH source factor significantly contributed (78%) to the measured ΣPAH. A five-factor PMF model dominated by fugitive dust sources explained 98% of PM10-2.5 mass and 86% of the ΣPAH. The predominant sources of PM10-2.5 mass were (i) Haul Road Dust (4.82 µg m-3; 53%), (ii) Mixed Fugitive Dust (2.89 µg m-3; 32%), (iii) Fugitive Oil Sand (0.88 µg m-3; 10%), Mobile Sources (0.23 µg m-3; 2%), and Organic Aerosol (0.06 µg m-3; 1%). Only the Organic Aerosol source significantly contributed (86%) to the measured ΣPAH.

Impacts of a large boreal wildfire on ground level atmospheric concentrations of PAHs, VOCs and ozone.

During May 2016 a very large boreal wildfire burned throughout the Athabasca Oil Sands Region (AOSR) in central Canada, and in close proximity to an extensive air quality monitoring network. This study examines speciated 24-h integrated polycyclic aromatic hydrocarbon (PAH) and volatile organic compound (VOC) measurements collected every sixth day at four and seven sites, respectively, from May to August 2016. The sum of PAHs (ΣPAH) was on average 17 times higher in fire-influenced samples (852 ng m-3, n = 8), relative to non-fire influenced samples (50 ng m-3, n = 64). Diagnostic PAH ratios in fire-influenced samples were indicative of a biomass burning source, whereas ratios in June to August samples showed additional influence from petrogenic and fossil fuel combustion. The average increase in the sum of VOCs (ΣVOC) was minor by comparison: 63 ppbv for fire-influenced samples (n = 16) versus 46 ppbv for non-fire samples (n = 90). The samples collected on August 16th and 22nd had large ΣVOC concentrations at all sites (average of 123 ppbv) that were unrelated to wildfire emissions, and composed primarily of acetaldehyde and methanol suggesting a photochemically aged air mass. Normalized excess enhancement ratios (ERs) were calculated for 20 VOCs and 23 PAHs for three fire influenced samples, and the former were generally consistent with previous observations. To our knowledge, this is the first study to report ER measurements for a number of VOCs and PAHs in fresh North American boreal wildfire plumes. During May the aged wildfire plume intercepted the cities of Edmonton (∼380 km south) or Lethbridge (∼790 km south) on four separate occasions. No enhancement in ground-level ozone (O3) was observed in these aged plumes despite an assumed increase in O3 precursors. In the AOSR, the only daily-averaged VOCs which approached or exceeded the hourly Alberta Ambient Air Quality Objectives (AAAQOs) were benzene (during the fire) and acetaldehyde (on August 16th and 22nd). Implications for local and regional air quality as well as suggestions for supplemental air monitoring during future boreal fires, are also discussed.

Mutagenicity and Lung Toxicity of Smoldering vs. Flaming Emissions from Various Biomass Fuels: Implications for Health Effects from Wildland Fires.

BACKGROUND: The increasing size and frequency of wildland fires are leading to greater potential for cardiopulmonary disease and cancer in exposed populations; however, little is known about how the types of fuel and combustion phases affect these adverse outcomes. OBJECTIVES: We evaluated the mutagenicity and lung toxicity of particulate matter (PM) from flaming vs. smoldering phases of five biomass fuels, and compared results by equal mass or emission factors (EFs) derived from amount of fuel consumed. METHODS: A quartz-tube furnace coupled to a multistage cryotrap was employed to collect smoke condensate from flaming and smoldering combustion of red oak, peat, pine needles, pine, and eucalyptus. Samples were analyzed chemically and assessed for acute lung toxicity in mice and mutagenicity in Salmonella. RESULTS: The average combustion efficiency was 73 and 98% for the smoldering and flaming phases, respectively. On an equal mass basis, PM from eucalyptus and peat burned under flaming conditions induced significant lung toxicity potencies (neutrophil/mass of PM) compared to smoldering PM, whereas high levels of mutagenicity potencies were observed for flaming pine and peat PM compared to smoldering PM. When effects were adjusted for EF, the smoldering eucalyptus PM had the highest lung toxicity EF (neutrophil/mass of fuel burned), whereas smoldering pine and pine needles had the highest mutagenicity EF. These latter values were approximately 5, 10, and 30 times greater than those reported for open burning of agricultural plastic, woodburning cookstoves, and some municipal waste combustors, respectively. CONCLUSIONS: PM from different fuels and combustion phases have appreciable differences in lung toxic and mutagenic potency, and on a mass basis, flaming samples are more active, whereas smoldering samples have greater effect when EFs are taken into account. Knowledge of the differential toxicity of biomass emissions will contribute to more accurate hazard assessment of biomass smoke exposures. https://doi.org/10.1289/EHP2200.

Chemical characterization and sources of PM2.5 at 12-hr resolution in Guiyang, China.

The increasing emission of primary and gaseous precursors of secondarily formed atmospheric particulate matter due to continuing industrial development and urbanization are leading to an increased public awareness of environmental issues and human health risks in China. As part of a pilot study, 12-hr integrated fine fraction particulate matter (PM2.5) filter samples were collected to chemically characterize and investigate the sources of ambient particulate matter in Guiyang City, Guizhou Province, southwestern China. Results showed that the 12-hr integrated PM2.5 concentrations exhibited a daytime average of 51 ± 22µg·m-3 (mean ± standard deviation) with a range of 17-128µg·m-3 and a nighttime average of 55 ± 32µg·m-33 with a range of 4-186 µg·m-3. The 24-hr integrated PM2.5 concentrations varied from 15 to 157 µg·m-3, with a mean value of 53 ± 25 µg·m-3, which exceeded the 24-hr PM2.5 standard of 35µg·m-3 set by USEPA, but was below the standard of 75µg·m-3, set by China Ministry of Environmental Protection. Energy-dispersive X-ray fluorescence spectrometry (XRF) was applied to determine PM2.5 chemical element concentrations. The order of concentrations of heavy metals in PM2.5 were iron (Fe) > zinc (Zn) > manganese (Mn) > lead (Pb) > arsenic (As) > chromium (Cr). The total concentration of 18 chemical elements was 13 ± 2 µg·m-3, accounting for 25% in PM2.5, which is comparable to other major cities in China, but much higher than cities outside of China.

The impact of the 2016 Fort McMurray Horse River Wildfire on ambient air pollution levels in the Athabasca Oil Sands Region, Alberta, Canada.

An unprecedented wildfire impacted the northern Alberta city of Fort McMurray in May 2016 causing a mandatory city wide evacuation and the loss of 2,400 homes and commercial structures. A two-hectare wildfire was discovered on May 1, grew to ~157,000ha by May 5, and continued to burn an estimated ~590,000ha by June 13. A comprehensive air monitoring network operated by the Wood Buffalo Environmental Association (WBEA) in and around Fort McMurray provided essential health-related real-time air quality data to firefighters during the emergency, and provided a rare opportunity to elucidate the impact of gaseous and particulate matter emissions on near-field communities and regional air pollution concentrations. The WBEA network recorded 188 fire-related exceedances of 1-hr and 24-hr Alberta Ambient Air Quality Objectives. Two air monitoring sites within Fort McMurray recorded mean/maximum 1-hr PM2.5 concentrations of 291/5229µgm-3 (AMS-6) and 293/3259µgm-3 (AMS-7) during fire impact periods. High correlations (r2=0.83-0.97) between biomass combustion related gases (carbon monoxide (CO), non-methane hydrocarbons (NMHC), total hydrocarbons (THC), total reduced sulfur (TRS), ammonia) and PM2.5 were observed at the sites. Filter-based 24-hr integrated PM2.5 samples collected every 6 days showed maximum concentrations of 267µgm-3 (AMS-6) and 394µgm-3 (AMS-7). Normalized excess emission ratios relative to CO were 149.87±3.37µgm-3ppm-1 (PM2.5), 0.274±0.002ppmppm-1 (THC), 0.169±0.001ppmppm-1 (NMHC), 0.104±0.001ppmppm-1 (CH4), 0.694±0.007ppbppm-1 (TRS), 0.519±0.040ppbppm-1 (SO2), 0.412±0.045ppbppm-1 (NO), 1.968±0.053ppbppm-1 (NO2), and 2.337±0.077ppbppm-1 (NOX). A subset of PM2.5 filter samples was analyzed for trace elements, major ions, organic carbon, elemental carbon, and carbohydrates. Sample mass reconstruction and fire specific emission profiles are presented and discussed. Potential fire-related photometric ozone instrument positive interferences were observed and were positively correlated with NO and NMHC.