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.

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.

Development of a thoracic personal sampler system for co-sampling of sulfuric acid mist and sulfur dioxide gas.

A novel personal sampler was designed to measure inorganic acid mists and gases for determining human exposure levels to these acids in workplaces. This sampler consists of (1) a parallel impactor for classifying aerosol by size following the ISO/CEN/ACGIH defined human thoracic fraction, (2) a cellulose filter to collect the residual acid mist but allowing penetration of sulfur dioxide gas, and (3) an accordion-shaped porous membrane denuder (aPMD) for adsorbing the penetrating sulfur dioxide gas. Acid-resistant PTFE was chosen as the housing material to minimize sampling interference. To test the performance of the parallel impactor, monodisperse aerosol was created by a vibrating orifice aerosol generator. The results showed that the penetration curve of the impactor run at 2 LPM flow rate agreed well with the defined thoracic fraction. Almost all sampling biases were within 10% for particle size distributions with MMAD between 1-25 µm and GSD between 1.75-4, which meets the criteria of the EN 13205 standard. To evaluate the performance of the aPMDs, sulfur dioxide gas was sourced directly from a cylinder. The aPMDs maintained a gas collection efficiency greater than 95% for 4 hr when sampling 8.6 ppm of sulfur dioxide gas. While the aPMD had similar performance to the commonly adopted annular or honeycomb denuders made of glass, this shatterproof aPMD is only half of the volume and 1/25th the weight of the honeycomb denuder. Testing of the entire sampler with a mixture of sulfuric acid mist and sulfur dioxide gas showed the system could sample both with negligible interference. All the test results illustrate that the new sampler, which is flat, lightweight, and portable, is suitable for personal use and is capable of a more accurate assessment of human exposure to inorganic acid mist and SO2 gas.

Ground-level air pollution changes during a boreal wildland mega-fire.

The 2011 Richardson wildland mega-fire in the Athabasca Oil Sands Region (AOSR) in northern Alberta, Canada had large effects on air quality. At a receptor site in the center of the AOSR ambient PM2.5, O3, NO, NO2, SO2, NH3, HONO, HNO3, NH4+ and NO3- were measured during the April-August 2011 period. Concentrations of NH3, HNO3, NO2, SO2 and O3 were also monitored across the AOSR with passive samplers, providing monthly summer and bi-monthly winter average values in 2010, 2011 and 2012. During the fire, hourly PM2.5 concentrations >450µgm-3 were measured at the AMS 1 receptor site. The 24-h National Ambient Air Quality Standard (NAAQS) of 35µgm-3 and the Canada Wide Standard (CWS) of 30µgm-3 were exceeded on 13days in May and 7days in June. During the fire emission periods, sharp increases in NH3, HONO, HNO3, NH4+, NO3- and total inorganic reactive N concentrations occurred, all closely correlated with the PM2.5 changes. There were large differences in the relative contribution of various N compounds to total inorganic N between the no-fire emission and fire emission periods. While in the absence of fires NO and NO2 dominated, their relative contribution during the fires was ~2 fold smaller, mainly due to increased NH3, NH4+ and NO3-. Concentrations of HONO and HNO3 also greatly increased during the fires, but their contribution to the total inorganic N pool was relatively small. Elevated NH3 and HNO3 concentrations affected large areas of northern Alberta during the Richardson Fire. While NH3 and HNO3 concentrations were not at levels considered toxic to plants, these gases contributed significantly to atmospheric N deposition. Generally, no significant changes in O3 and SO2 concentrations were detected and their ambient concentrations were below levels harmful to human health or sensitive vegetation.

Atmospheric dry deposition of sulfur and nitrogen in the Athabasca Oil Sands Region, Alberta, Canada.

Due to the potential ecological effects on terrestrial and aquatic ecosystems from atmospheric deposition in the Athabasca Oil Sands Region (AOSR), Alberta, Canada, this study was implemented to estimate atmospheric nitrogen (N) and sulfur (S) inputs. Passive samplers were used to measure ambient concentrations of ammonia (NH3), nitrogen dioxide (NO2), nitric acid/nitrous acid (HNO3/HONO), and sulfur dioxide (SO2) in the AOSR. Concentrations of NO2 and SO2 in winter were higher than those in summer, while seasonal differences of NH3 and HNO3/HONO showed an opposite trend, with higher values in summer. Concentrations of NH3, NO2 and SO2 were high close to the emission sources (oil sands operations and urban areas). NH3 concentrations were also elevated in the southern portion of the domain indicating possible agricultural and urban emission sources to the southwest. HNO3, an oxidation endpoint, showed wider ranges of concentrations and a larger spatial extent. Concentrations of NH3, NO2, HNO3/HONO and SO2 from passive measurements and their monthly deposition velocities calculated by a multi-layer inference model (MLM) were used to calculate dry deposition of N and S. NH3 contributed the largest fraction of deposited N across the network, ranging between 0.70-1.25kgNha(-1)yr(-1), HNO3/HONO deposition ranged between 0.30-0.90kgNha(-1)yr(-1), and NO2 deposition between 0.03-0.70kgNha(-1)yr(-1). During the modeled period, average dry deposition of the inorganic gaseous N species ranged between 1.03 and 2.85kgNha(-1)yr(-1) and SO4-S deposition ranged between 0.26 and 2.04kgha(-1)yr(-1). Comparisons with co-measured ion exchange resin throughfall data (8.51kgSha(-1)yr(-1)) indicate that modeled dry deposition combined with measured wet deposition (1.37kgSha(-1)yr(-1)) underestimated S deposition. Gas phase NH3 (71%) and HNO3 plus NO2 (79%) dry deposition fluxes dominated the total deposition of NH4-N and NO3-N, respectively.

Collocated comparisons of continuous and filter-based PM2.5 measurements at Fort McMurray, Alberta, Canada.

UNLABELLED: Collocated comparisons for three PM(2.5) monitors were conducted from June 2011 to May 2013 at an air monitoring station in the residential area of Fort McMurray, Alberta, Canada, a city located in the Athabasca Oil Sands Region. Extremely cold winters (down to approximately -40°C) coupled with low PM(2.5) concentrations present a challenge for continuous measurements. Both the tapered element oscillating microbalance (TEOM), operated at 40°C (i.e., TEOM(40)), and Synchronized Hybrid Ambient Real-time Particulate (SHARP, a Federal Equivalent Method [FEM]), were compared with a Partisol PM(2.5) U.S. Federal Reference Method (FRM) sampler. While hourly TEOM(40) PM(2.5) were consistently ~20-50% lower than that of SHARP, no statistically significant differences were found between the 24-hr averages for FRM and SHARP. Orthogonal regression (OR) equations derived from FRM and TEOM(40) were used to adjust the TEOM(40) (i.e., TEOM(adj)) and improve its agreement with FRM, particularly for the cold season. The 12-year-long hourly TEOM(adj) measurements from 1999 to 2011 based on the OR equations between SHARP and TEOM(40) were derived from the 2-year (2011-2013) collocated measurements. The trend analysis combining both TEOM(adj) and SHARP measurements showed a statistically significant decrease in PM(2.5) concentrations with a seasonal slope of -0.15 µg m(-3) yr(-1) from 1999 to 2014. IMPLICATIONS: Consistency in PM(2.5) measurements are needed for trend analysis. Collocated comparison among the three PM(2.5) monitors demonstrated the difference between FRM and TEOM, as well as between SHARP and TEOM. The orthogonal regressions equations can be applied to correct historical TEOM data to examine long-term trends within the network.

Measurement of fine particulate matter water-soluble inorganic species and precursor gases in the Alberta Oil Sands Region using an improved semicontinuous monitor.

UNLABELLED: The ambient ion monitor-ion chromatography (AIM-IC) system, which provides hourly measurements of the main chemical components of PM2.5 (particulate matter with an aerodynamic diameter<2.5 µm) and its precursor gases, was evaluated and deployed from May to July 2011 and April to December 2013 in the Athabasca Oil Sands Region (AOSR) of northeastern Alberta, Canada. The collection efficiencies for the gas-phase SO2 and HNO3 using the cellulose membrane were 96% and 100%, respectively, and the collection efficiency of NH3 using the nylon membrane was 100%. The AIM-IC was compared with a collocated annular denuder sampling system (ADSS) and a Federal Reference Method (FRM) Partisol PM2.5 sampler. The correlation coefficients of SO4(2-) concentrations between the AIM-IC and ADSS and between the AIM-IC and the Partisol PM2.5 sampler were 0.98 and 0.95, respectively. The comparisons also showed no statistically significant difference between the measurement sets, suggesting that the AIM-IC measurements of the PM2.5 chemical composition are comparable to the ADSS and Partisol PM2.5 methods. NH3 concentration in the summer (mean±standard deviation, 1.9±0.7 µg m(-3)) was higher than in the winter (1.3±0.9 µg m(-3)). HNO3 and NO3- concentrations were generally low in the AOSR, and especially in the winter months. NH4+ (0.94±0.96 µg m(-3)) and SO4(2-) (0.58±0.93 µg m(-3)) were the major ionic species of PM2.5. Direct SO2 emissions from oil sands processing operations influenced ambient particulate NH4+ and SO4(2-) values, with hourly concentrations of NH4+ and SO4(2-) measured downwind (~30 km away from the stack) at 10 and 28 µg m(-3). During the regional forest fire event in 2011, high concentrations of NO3-, NH4+, HNO3, NH3, and PM2.5 were observed and the corresponding maximum hourly concentrations were 31, 15, 9.6, 89, and >450 (the upper limit of PM2.5 measurement) µg m(-3), suggesting the formation of NH4NO3. IMPLICATIONS: The AOSR in Canada is one of the most scrutinized industrial regions in the developed world due to the extent of oil extraction activities. Because of this, it is important to accurately assess the effect of these operations on regional air quality. In this study, we compare a new analytical approach, AIM-IC, with more standard analytical approaches to understand how local anthropogenic and nonanthropogenic sources (e.g., forest fires) impact regional air quality. With this approach, we also better characterize PM2.5 composition and its precursor gases to understand secondary aerosol formation mechanisms and to better identify possible control techniques if needed.

PAH Measurements in Air in the Athabasca Oil Sands Region.

Polycyclic aromatic hydrocarbon (PAH) measurements were conducted by Wood Buffalo Environmental Association (WBEA) at four community ambient Air quality Monitoring Stations (AMS) in the Athabasca Oil Sands Region (AOSR) in Northeastern Alberta, Canada. The 2012 and 2013 mean concentrations of a subset of the 22 PAH species were 9.5, 8.4, 8.8, and 32 ng m(-3) at AMS 1 (Fort McKay), AMS 6 (residential Fort McMurray), AMS 7 (downtown Fort McMurray), and AMS 14 (Anzac), respectively. The average PAH concentrations in Fort McKay and Fort McMurray were in the range of rural and semirural areas, but peak values reflect an industrial emission influence. At these stations, PAHs were generally associated with NO, NO2, PM2.5, and SO2, indicating the emissions were from the combustion sources such as industrial stacks, vehicles, residential heating, and forest fires, whereas the PAH concentrations at AMS 14 (∼35 km south of Fort McMurray) were more characteristic of urban areas with a unique pattern: eight of the lower molecular weight PAHs exhibited strong seasonality with higher levels during the warmer months. Enthalpies calculated from Clausius-Clapeyron plots for these eight PAHs suggest that atmospheric emissions were dominated by temperature-dependent processes such as volatilization at warm temperatures. These findings point to the potential importance of localized water-air and/or surface-air transfer on observed PAH concentrations in air.

Control of Cr6+ emissions from gas metal arc welding using a silica precursor as a shielding gas additive.

Hexavalent chromium (Cr(6+)) emitted from welding poses serious health risks to workers exposed to welding fumes. In this study, tetramethylsilane (TMS) was added to shielding gas to control hazardous air pollutants produced during stainless steel welding. The silica precursor acted as an oxidation inhibitor when it decomposed in the high-temperature welding arc, limiting Cr(6+) formation. Additionally, a film of amorphous SiO(2) was deposited on fume particles to insulate them from oxidation. Experiments were conducted following the American Welding Society (AWS) method for fume generation and sampling in an AWS fume hood. The results showed that total shielding gas flow rate impacted the effectiveness of the TMS process. Increasing shielding gas flow rate led to increased reductions in Cr(6+) concentration when TMS was used. When 4.2% of a 30-lpm shielding gas flow was used as TMS carrier gas, Cr(6+) concentration in gas metal arc welding (GMAW) fumes was reduced to below the 2006 Occupational Safety and Health Administration standard (5 µg m(-3)) and the efficiency was >90%. The process also increased fume particle size from a mode size of 20 nm under baseline conditions to 180-300 nm when TMS was added in all shielding gas flow rates tested. SiO(2) particles formed in the process scavenged nanosized fume particles through intercoagulation. Transmission electron microscopy imagery provided visual evidence of an amorphous film of SiO(2) on some fume particles along with the presence of amorphous SiO(2) agglomerates. These results demonstrate the ability of vapor phase silica precursors to increase welding fume particle size and minimize chromium oxidation, thereby preventing the formation of hexavalent chromium.

Method for contamination of filtering facepiece respirators by deposition of MS2 viral aerosols.

A droplet/aerosol loading chamber was designed to deliver uniform droplets/aerosols onto substrates. An ultrasonic nebulizer was used to produce virus-containing droplets from artificial saliva to emulate those from coughing and sneezing. The operating conditions were determined by adjusting various parameters to achieve loading density and uniformity requirements. The count median diameter and mass median diameter were 0.5-2 and 3-4 µm, respectively, around the loading location when 35% relative humidity was applied. The average loading density was ∼2×103 plaque-forming units/cm2 for 5-min loading time with a virus titer of 107 plaque-forming units/mL. Six different filtering facepiece respirators from commercial sources were loaded to evaluate uniform distribution. For each of the six FFRs, the virus loading uniformity within a sample and across numerous samples was 19.21% and 12.20%, respectively. This system supports a standard method for loading viable bioaerosols onto specimen surfaces when different decontamination techniques are to be compared.

Minimization of artifacts in sulfuric acid mist measurement using NIOSH Method 7903.

NIOSH Method 7903 employs a silica gel tube for sulfuric acid mist measurement in workplaces. However, SO2 gas present in the sample volume can be transformed into sulfate in the sampling process causing an artifact that is reported as sulfuric acid. A sampling train incorporating a honeycomb denuder system was applied for field sampling at seven phosphate fertilizer plants to evaluate its use for reducing the artifact sulfate concentration while preserving the actual sulfuric acid mist concentration. The denuder system was designed to remove SO2 gas before the air entered the silica gel tube and to monitor SO2 concentration at the same time. A deactivation model was also applied to correct for the presence of the artifact. The denuder system had 95.7 +/- 6.8% collection efficiency for SO2 gas, and the impact of sulfate aerosol on SO2 collection was negligible. SO2 concentrations at the seven plants ranged from 34 ppb to 5.6 ppm. The honeycomb denuder system and the deactivation model were shown to reduce the artifact sulfate concentration by 70% and 39%, respectively. However, they were still higher than the sulfate aerosol concentration measured by a cascade impactor. One possible reason is the residual sulfate in the glass fiber filter and the silica gel.

Positive artifact sulfate formation from SO2 adsorption in the silica gel sampler used in NIOSH Method 7903.

NIOSH Method 7903, which uses one section of glass fiber filter and two sections of silica gel, has been developed to determine the total concentrations of acid mists in workplace air, although certain gases are suspected to cause interference. In this study, experiments were performed to investigate the roles of sulfur(IV) oxidation and sulfur dioxide (SO2) adsorption in causing artifacts in sulfuric acid measurement. First, sulfur(IV) oxidation, under four combinations of water bath temperature and Na2CO3 solution concentration, was examined to investigate the effect of the extraction process of NIOSH Method 7903. It was shown that sulfur(IV) oxidation to form sulfate could reach 100% within just 2-3 min, following the extraction process of NIOSH Method 7903. The results demonstrate that, using the procedure, SO2 adsorbed by the silica gel and the glass fiber filter easily yields artifact sulfate. Sulfur dioxide adsorption under various flow rates, SO2 concentrations, and sampling times was also investigated. The experimental data were fitted to a deactivation model to determine the adsorption rate constant and the deactivation rate constant. The model can serve as a tool for estimating the artifact sulfate if the SO2 concentration is available.

Chemical characteristics of aerosol mists in phosphate fertilizer manufacturing facilities.

Of the carcinogens listed by the National Toxicology Program (NTP), strong inorganic mists containing sulfuric acid were identified as a known human carcinogen. In this study, aerosol sampling was conducted at 24 locations in eight Florida phosphoric acid and concentrated fertilizer manufacturing plants and two locations as background in Winter Haven and Gainesville, Florida, using dichotomous samplers. The locations were selected where sulfuric acid mist may potentially exist, including sulfuric acid pump tank areas, belt or rotating table phosphoric acid filter floors, sulfuric acid truck loading/unloading stations, phosphoric acid production reactors (attack tanks), and a concentrated fertilizer granulator during scrubbing with a weak sulfuric acid mixture. An ion chromatography system was used to analyze sulfate and other water soluble ion species. In general, sulfate, fluoride, ammonium, and phosphate were the major species in the fertilizer facilities. For the rotating table/belt phosphoric acid filter floor, phosphate and fluoride were the dominant species for PM10, and the maximum concentrations were 170 and 106 microg/m3, respectively. For the attack tank, fluoride was the dominant species for PM10, and the maximum concentration was 462 microg/m3. At the sulfuric acid pump tank, sulfate was the dominant species, and the maximum PM10 sulfate concentration was 181 microg/m3. The concentration of PM10 sulfate including ammonium sulfate, calcium sulfate, and sulfuric acid were lower than 0.2 mg/m3 at all locations. The aerosols at the filter floor and the attack tank were acidic. The coarse mode aerosol at the sulfuric acid pump tank (an outdoor location) was acidic, whereas the fine mode aerosol was neutral to basic.

Size-resolved sulfuric acid mist concentrations at phosphate fertilizer manufacturing facilities in Florida.

Strong inorganic acid mists containing sulfuric acid were identified as a 'known human carcinogen' in a National Toxicology Program (NTP) report where phosphate fertilizer manufacture was listed as one of many occupational exposures to strong acids. To properly assess the occupational exposure to sulfuric acid mists in modern facilities, approved National Institute for Occupational Safety and Health (NIOSH) Method 7903 and a cascade impactor were used for measuring the total sulfuric acid mist concentration and size-resolved sulfuric acid mist concentration, respectively. Sampling was conducted at eight phosphate fertilizer plants and two background sites in Florida and there were 24 sampling sites in these plants. Samples were analyzed by ion chromatography (IC) to quantify the water-soluble ion species. The highest sulfuric acid concentrations by the cascade impactor were obtained at the sulfuric acid pump tank area. When high aerosol mass concentrations (100 micro g m(-3)) were observed at this area, the sulfuric acid mists were in the coarse mode. The geometric mean sulfuric acid concentrations (+/-geometric standard deviation) of PM(23) (aerodynamic cut size smaller than 23 micro m), PM(10) and PM(2.5) from the cascade impactor were 41.7 (+/-5.5), 37.9 (+/-5.8) and 22.1 (+/-4.5) micro g m(-3), respectively. The geometric mean (+/-geometric standard deviation) for total sulfuric acid concentration from the NIOSH method samples was 143 (+/-5.08) micro g m(-3). Sulfuric acid mist concentrations varied significantly among the plants and even at the same location. The measurements by the NIOSH method were 1.5-229 times higher than those by the cascade impactor. Moreover, using the NIOSH method, the sulfuric acid concentrations measured at the lower flow rate (0.30 Lpm) were higher than those at the higher flow rate (0.45 Lpm). One possible reason for the significant differences between the results from the cascade impactor and the NIOSH method is the potential artifact resulting from the interaction of SO(2) with silica gel and glass fiber used in the NIOSH method.