Appendices for:

Source Apportionment of Ambient Fine and Coarse Particulate Matter Polycyclic Aromatic Compounds at the Bertha Ganter - Fort McKay Community Site, Alberta, Canada

Matthew S. Landis*, J. Patrick Pancras, Joseph R. Graney, Emily M. White, Eric S. Edgerton*Corresponding author; phone: (919) 214-0341; mlandis@atmospheric-solutions.com

Appendix A: Magee Model AE-22 Aethalometer Measurement and Compensation Discussion

Appendix B: Quartz Filter and PUF/XAD Sample Extraction and Analysis

Appendix C: TablesTable C.1: Study GC-TOF-MS PAH and PAC Method Detection Limits.Table C.2: Inorganic MDL and Percent above MDL, by Analyte and Size Fraction.Table C.3: Bertha Ganter Fort McKay Site Alberta Ambient Air Quality Objectives (AAAQO) Exceedances

(October 20, 2014 – October 27, 2015).Table C.4: Ambient PAH Concentrations Collected on PUF/XAD and TSP samples (ng m-3).Table C.5: Ambient PAC Concentrations Collected on PUF/XAD and TSP samples (ng m-3).Table C.6: PM10 PAH & PAC Analytical Precision from Replicate Analysis (n = 29).Table C.7: PM2.5 PAH & PAC Analytical Precision from Replicate Analysis (n = 29).Table C.8: PAH and PAC Field Blanks for PM, TSP, and PUF/XAD (ng sample-1).

Appendix D: FiguresFigure D.1: Comparison of the Dichotomous Sampler and SHARP Instrument PM2.5 Mass at Bertha Ganter

Fort McKay Monitoring Site (Oct. 20, 2014 – Oct. 27, 2015).Figure D.2: Relative Frequency Histograms of Dichotomous Sampler PM2.5 (a) and PM10-2.5 (b) Mass at Bertha

Ganter Fort McKay Monitoring Site (Oct. 20, 2014 – Oct. 27, 2015).Figure D.3: Time Series of Bertha Gartner Fort McKay PM2.5 Monthly Geometric Mean Mass Concentrations

(the Study Period is Shown Inside Blue Box).Figure D.4: Relationship Between Hourly Median PM2.5, BC, UVPM and UVPM/BC Ratio at Bertha Ganter

Fort McKay During the Study Period (October 2014 – October 2015).Figure D.5: Time Series of Hourly PM2.5 Mass, BC, and UVPM at Bertha Ganter Fort McKay during Wildland

Fire Event Impacts.Figure D.6: Time Series of Hourly PM2.5 Mass, BC, and Ammonia at Bertha Ganter Fort McKay during

Wildland Fire Event Impacts.Figure D.7: Relationship Between Hourly PM2.5 Mass when Concentrations were > 40 g m-3 and Delta-C,

Total Reduced Sulfur, and Ammonia at Bertha Ganter-Fort McKay Site.Figure D.8: Relationship between Hourly Delta-C and PM2.5 Mass during July 3-4, 2015 Wildland Fire Event

at Bertha Ganter Fort McKay (n = 35 Hourly Observations).Figure D.9: Relationship between Hourly Delta-C and PM2.5 Mass during July 11-12, 2015 Wildland Fire

Event at Bertha Ganter Fort McKay (n = 37 Hourly Observations).Figure D.10: Particle-Vapor Phase Partitioning of PAHs and PACs by Season.Figure D.11: Relative Contributions of Individual PAHs to Total PAHs in TSP + PUF/XAD.Figure D.12: Relative Contribution of Individual PACs to Total PACs in TSP + PUF/XAD.Figure D.13: Comparison of Ambient Particulate Phase PAHs and PACs in TSP versus PM10.Figure D.14: Box and Whisker Plots for PM2.5 (a) and PM10-2.5 (b) Trace Elements (ng m-3).Figure D.15: PM2.5 to PM10-2.5 Ratios for Mass and Trace Elements (Based on Study Means).Figure D.16: 24-hour Average PM2.5 and PM10-2.5 Mass (g m-3).Figure D.17: 24-hour Average PM2.5 and PM10-2.5 Sulfur Concentrations.Figure D.18: Daily Average Concentrations of Aluminum, Iron and Potassium (ng m-3).Figure D.19: Daily Average Concentrations of Cadmium, Lead and Molybdenum (ng m-3).Figure D.20: SWIM Model Spatial Source Probability for NH3.

Appendix A: Magee Model AE-22 Aethalometer Measurement and Compensation Discussion

The Magee Scientific (Berkeley, CA) Model AE-22 Aethalometer (Hansen et al., 1984) was deployed at the Wood Buffalo Environmental Association (WBEA) Bertha Ganter-Fort McKay (BGFM) ambient air monitoring station as part of this study to provide real-time black carbon (BC) PM2.5

concentrations in ambient air. The Aethalometer instrument measures the transmitted light intensities through the ‘sensing’ portion of the filter tape, on which the aerosol spot is being collected, and a “reference” portion of the filter tape, as a check on the stability of the optical source. The sampling tape is automatically advanced when a preset optical attenuation set point of the filter spot is reached. The Aethalometer calculates one new aerosol BC concentration reading every time base period (set to 1 minute during this study). BC (“soot”) is emitted from all types of combustion sources, most notably from diesel combustion exhaust and biomass burning (Cooke and Wilson, 1996; Sandradewi et al., 2008). The Model AE-22 Aethalometer measures the light absorption of carbon particles at two wavelengths: 880 nm infrared (IR), quantitative for the mass of BC; and 370 nm ultraviolet (UVPM). Biomass smoke is known to contain relatively high concentrations of organic aerosols such as polycyclic aromatic hydrocarbons (PAHs), aromatics, and humic-like substances (Hoffer et al., 2006; Kochbach et al., 2006; Alfarra et al., 2007; Weimer et al., 2008), which enhances the absorption of light in the UV wavelength band in comparison to BC that dominates the adsorption in the IR band (Jeong et al., 2004; Sandradewi et al., 2008; Wang et al., 2011). Heavy-duty vehicle emission aerosols from diesel fuel combustion contain a higher fraction of BC than organic material (Fruin et al., 2004; Burtscher, 2005); so, the ratio of UVPM/BC wavelength light adsorption measured by the Aethalometer can be diagnostic for local biomass burning smoke emissions (Sandradewi et al., 2008).

Optical saturation (a loading effect) leads to the Aethalometer-reported BC concentrations decreasing with increased attenuation (ATN, a measure of the light absorption by the deposited aerosol) even when the measured aerosol has a constant BC concentration (Gundel et al., 1984). This phenomenon requires the post processing of the AE-22 Aethalometer data to correct the ambient BC concentrations based on a dynamic bin compensation methodology proposed by Park et al. (2010). Typically, the compensation adjustment is relatively small, however, when impacted by biomass combustion smoke the correction can be substantial. For this study we used a software program produced by the Air Quality Laboratory at Washington University in St. Louis (WUAQL) called AethDataMasher version 7.1. The goal of the Bin method algorithm is to regress out the decreasing BC concentration trend as ATN increases so that, on average, BC concentration is independent of ATN. The loading effect is assumed to follow the form detailed in Equation 1.

BCt BCr (1+ k . ATN) (1)

where BCt is the true concentration, BCr is the Magee AE-22 Aethalometer-reported concentration, and k is an empirical adjustment parameter that, in this algorithm, is obtained from the regression of concentration on ATN.

The AethDataMasher programs first step is to bin the raw concentration data (1-minute averaged) by attenuation. The algorithm allows the user to specify either a fixed bin width (e.g., 5 ATN units) or an approximate number of bins to be equally distributed over the attenuation range observed for each wavelength channel. The default is a fixed bin width of 5 ATN units. Tape advances are followed by an instrument stabilization period with no data reported. The time duration of all data gaps is identified and the mode gap size (e.g., three consecutive one-minute missing records) is used to flag the tape advances in the time series. If the second mode data gap occurs with frequency greater than 5% of the first mode data gap, the user is prompted to include or exclude the second mode data gaps as tape advances.

Data recorded between each tape advance are stratified into the ATN bins and the mean concentration is calculated for each bin (TAC values). These bin-specific mean concentration values are then normalized to the average concentration over all the bins populated for that tape advance (TAN values). Next, these normalized, binned concentrations are aggregated over a user-specified number of tape advances w (default w = 30) and the median value is calculated for each bin. The previous normalization step is performed to remove concentration differences across the w tapes advances because the goal is to have the bin-specific median values reflect the concentration change with ATN rather with minimal influence for variations in the ambient concentration over the w tape advances.

Bin-specific median values are regressed on ATN to determine the empirical data adjustment parameter, k. Error bars denote the interquartile ranges about the median normalized concentrations. The open circles show the median normalized concentrations estimated from Equation 1 using the fitted k-value. Ideally these values should be tightly clustered about the horizontal line at normalized concentration of unity (e.g., the ATN dependence of concentration has been removed) and in this example they are biased high by up to 2%. The analysis is actually performed with a user-specified centered window for the number of data traces between tape advances (w) used to calculate the median normalized concentrations. A regression to determine k is performed for each tape advance except the first w/2 and last w/2 records. These spin-up and spin-down periods are imputed with the first- and last-calculated k-values, respectively. Given the smoothed time series of k-values, the raw data are adjusted using Equation 1 with the smoothed k-value for tape advance j used to adjust all data between tape advances j and j+1. The overall process is repeated for each channel of data in addition to the 880 nm BC data (e.g., the 370 nm UVPM data for the BGFM site AE-22 two channel Aethalometer).

Appendix Figure D.1 and Appendix Figure D.2 show the raw and bin method compensated BC and UVPM concentrations for data collected at the Bertha Ganter-Fort McKay ambient air monitoring station on July 4, 2015, respectively during a wildfire impact period. Over this time period both the BC and UVPM concentrations were decreasing and it appears the bin compensation algorithm successfully removed the ATN dependency in the data from both wavelength channels and the resulting 1-minute resolution data look reasonable.

Appendix A. Bibliography

Alfarra, M.R., Prevot, A.S.H., Szidat, S., Sandradewi, J., Weimer, S., Lanz, V.A., Schreiber, D., Mohr, M., Baltensperger, U., 2007. Identification of the mass spectral signature of organic aerosols from wood burning emissions. Environ. Sci. Technol., 41:5770–5777.

Burtscher, 2005. Physical characterization of particulate emissions from diesel engines: a review. Journal of Aerosol Science, 36:896-932.

Cooke, W.F., Wilson, J.J.N., 1996. A global black carbon aerosol model. J. Geophys. Res., 101:19395-19409.

Fruin, S.A., Winer, A.M., Rodes, C.E., 2004. Black carbon concentrations in California vehicles and estimation of in-vehicle diesel exhaust particulate matter exposures. Atmos. Environ. 38:4123-4133.

Gundel, L.A., Dod, R.L., Rosen, H., Novakov, T., 1984. The relationship between optical attenuation and black carbon concentration for ambient and source particles. Sci. Total Environ., 36:197-202.

Hansen, A.D.A., Rosen, H., Novakov, T., 1984. The Aethalometer – an instrument for the real-time measurement of optical-absorption by aerosol-particles. Sci. Total Environ., 36:191-196.

Hoffer, A., Gelencer, A., Guyon, P., Kiss, G., Schmid, O., Frank, G., Artaxo, P., Andreae, M.O., 2006. Optical properties of humic-like substances (HULIS) in biomass-burning aerosols. Atmos. Chem. Phys. 6:3563-3570.

Jeong, C.H., Hopke, P.K., Kim, E., Lee, D.W., 2004. The comparison between thermal-optical transmittance elemental carbon and Aethalometer black carbon measured at multiple monitoring sites. Atmos. Environ., 38:5193-5204.

Kochbach, A., Li, Y., Yttri, K.E., Cassee, F.R., Schwarze, P.E., Namork, E., 2006. Physiochemical characterization of combustion particles from vehicle exhaust and residential wood smoke. Particle Fibre Toxicol 3:1.

Park, S.S., Hansen, A., Cho, S.Y., 2010. Measurement of real time black carbon for investigating spot loading effects of Aethalometer data. Atmos. Environ., 44:1449-1455.

Sandradewi, Prevot, A.S.H., Szidat, S., Perron, N., Alfarra, M.R., Lanz, V.A., Weingartner, E., Baltensperger, W., 2008. Using aerosol light absorption measurements for the quantitative determination of wood burning and traffic emission contributions to particulate matter. Environ. Sci. Technol., 42:3316-3323.

Wang, Y., Hopke, P.K., Rattigan, O.V., Xia, X., Chalupa, D.C., Utell, M.J., 2011a. Characterization of residential wood combustion particles using the two-wavelength Aethalometer. Environ. Sci. Technol., 45:7387-7393.

Weimer, S., Alfarra, M.R., Schreiber, D., Mohr, M., Prevot, A.S.H., Baltensperger, U., 2008. Organic aerosol mass spectral signatures from wood burning emissions: Influence of burning conditions and wood type. Journal of Geophysical Research, 113:D10304.

Appendix B: Quartz Filter and PUF/XAD Sample Extraction and Analysis

Quartz Filter and PUF/XAD Sample Extraction

For consistency with our existing methodology for the determination of polycyclic aromatic hydrocarbons (PAHs) and Polycyclic aromatic compounds (PACs) in lichens, we adapted our method of cyclohexane extraction, silica gel cleanup, and analysis by gas chromatograph mass spectroscopy (GC-MS; Studabaker et al., 2017) to the analysis of PM2.5 and PM10 filters. This approach is one of a number in use by European Union air quality reference laboratories (Ballesta et al., 2014). Filter extractions were performed in small batches of 10 sample filters. A method blank and control (using unused filters) were prepared for each batch. Each sample filter was placed in a 66 mL stainless steel extraction cell and spiked with Cambridge Isotope Laboratories (Cambridge, MA) CARB Method 429 PAH cocktail (# ES-2528) internal standard (25 ng each of deuterium-labeled Acenaphthene, Acenaphthylene, Anthracene, Benz[a]anthracene, Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[g,h,i]perylene, Benzo[a]pyrene, Chrysene, Dibenz[a,h]anthracene, Fluoranthene, Fluorene, Indeno[1,2,3-cd]pyrene, Naphthalene, Phenathrene, and Pyrene). Method controls were also spiked with target compounds (AccuStandard, New Haven, CT, and Chiron, Trondheim, Norway) at 25 ng per filter. The filters were extracted three times with pesticide grade cyclohexane (ThermoFisher, Sunnyvale, CA) at 100⁰C using a Dionex (Sunnyvale, CA) Model 300 accelerated solvent extractor (ASE). Extracts (totaling 110 - 130 mL) were concentrated on a TurboVap II (Biotage Charlotte, NC), then the volume for each sample was adjusted to 1 mL and transferred to a GC autosampler vial. Initial screening indicated that no sample cleanup was required.

Total suspended particulate (TSP) filters and polyurethane foam (PUF)/hydrophobic crosslinked adsorbent polystyrene copolymer resin (XAD) media were extracted separately to discriminate between particle-bound and vapor-phase PAHs and PACs. All extractions were performed by ERG according to U.S. Environmental Protection Agency method TO-13a (U.S. EPA, 1999). The entire 90 mm quartz fiber filter was used for extraction. Filters were placed in stainless steel extraction cells and spiked with an internal standard, and the void volume was taken up with sand. XAD from the same sample was placed in a second cell, one piece of PUF plug was placed on top and spiked with an internal standard, and the second piece of PUF was placed on top of it. Any void volume remaining was filled with sand. The Cambridge Isotope Laboratories CARB Method 429 PAH cocktail internal standard solution used for spiking both PUF/XAD and quartz filter media were provided to ERG by RTI. The media were extracted with a Dionex ASE with 20 ml of hexane/acetone (70/30) at 100°C and 1200 PSI. Samples were then concentrated by blowing down under an ultra-high purity (UHP) nitrogen gas stream to 1 mL, and the PUF/XAD sample extracts were cleaned up with silica gel solid phase extraction (SPE) cartridges prior to analysis. Filter and PUF/XAD extracts were stored at -20⁰C in a dedicated laboratory freezer prior to analysis.

PAH & PAC Analytical Methods

Analysis of filter and PUF/XAD extracts for PAHs and PACs were performed on a LECO (St. Joseph, MI) Pegasus 4D gas chromatograph with time-of-flight mass spectral detection (GC-TOF-MS) as described in Studabaker et al. (2017). The GC-TOF-MS was calibrated using standards up to 250 ng mL-1 (nine levels) for PACs and 2500 ng mL-1 for PAHs (12 levels). In addition to the unique compounds 1-methylnaphthalene, 2-methylnaphthalene, dibenzothiophene, and the biomass combustion marker retene, a single compound was selected as representative of each PAC group for generation of a calibration curve. Linear fit with 1/x weighting was used, with correlations yielding r2

> 0.99. Each analyte on the curve was quantified to within 10% of its nominal value. In all analytical runs, up to ten samples (including blanks and controls) were bracketed by solvent blanks and continuing calibration verification (CCV) standards at one (usually 12.5 ng mL-1) or more

concentrations. Solvent blanks were at or near noise level and showed no evidence of carryover. CCVs were required to be with 15% of the nominal value to pass quality assurance criteria. In addition, each batch included an independent source calibration check standard (25 ng mL-1) for each of the EPA 16 PAHs, and one duplicate injection to assess analytical precision.

PACs refer to C1 and C2 alkyl PAHs, dibenzothiophene, and the alkyl dibenzothiophenes. Alkyl PAHs are assigned to groups and named based on the level of alkylation of the parent PAH or a member of a group of structural isomers. Thus, methylfluoranthenes and methylpyrenes are included in the C1-fluoranthenes, while dimethylphenanthrenes and ethylphenanthrenes are included in the C2-phenanthrenes, up to C4-PAHs for some PAHs (Wang and Fingas, 2003). For analytical reasons (Studabaker et al., 2017) we limited our investigation to dibenzothiophene and C1 and C2 PACs. Retene (a C4-phenanthrene) was also included because it is a tracer species for softwood combustion (Ramdahl 1983; Schauer et al., 1996; Simoneit 2002).

Method detection limits (MDLs) of both PM10/PM2.5 and TSP/PUF/XAD were determined from laboratory blank data. MDLs were calculated as t0.01,(n-1) × standard deviation of the 28 PM and 16 TSP and PUF/XAD laboratory blank values for each analyte, and are shown in Appendix Table C.1. Instrument precision for samples was determined by duplicate injections, one per batch, across 29 batches for the 8” x 10” filters. Results are presented in Appendix Table C.6 for PM10, and in Appendix Table C.7 for PM2.5. The values range from < 10% to > 40%, with most falling in the range of 10% to 30%. Even though some analytes had lower-end calibration points dropped due to low sensitivity, all PAH and PAC analyte calibrations included at least six standard concentrations, and were linear over up to three orders of magnitude of instrument response, with r2 > 0.998. The lower limit of quantitation for each compound was in the range 1.25 - 5 ng per sample. Recoveries of PAHs and PACs spiked onto filters were generally acceptable (target recovery 70% - 130%). Exceptions were volatile compounds eluting before phenanthrene, and benzo(a)pyrene and its alkylated homologs. Field blank data for both PM and TSP/PUF/XAD samples indicated a significant contamination by volatile-phase compounds and are summarized in Appendix Table C.8. Four PM trip blanks, which were returned to RTI between the field blank sampling events of September 29, 2015 and October 22, 2015, yielded much lower concentrations of almost all analytes compared to either of those events.

Appendix B. BibliographyBallesta, P.P., Grandesso, E., Kowalewski, K., 2014. European interlaboratory comparison exercise for the analysis of PAHs on PM10 quartz filters. J. Geophys. Res.: Atmos., 119:3486-3499.

Ramdahl, T., 1983. Retene-a molecular marker of wood combustion in ambient air, Nature, 306:580-582.

Schauer, J.J., Rogge, W.F., Hildemann, L.M., Mazurek, M.A., Cass, G.R., 1996. Source apportionment of airborne particulate matter using organic compounds as tracers. Atmos. Environ., 30:3837-3855.

Simoneit, B.R.T., 2002. Biomass burning – a review of organic tracers for smoke from incomplete combustion. Applied Geochemistry, 17:129-162.

Studabaker, W., Puckett, K.J., Percy, K.E., Landis, M.S., 2017. Determination of polynuclear aromatic hydrocarbons, dibenzothiophene, and alkylated homologs in the lichen Hypogymnia physodes by gas chromatography using single quadrupole mass spectroscopy and time-of-flight mass spectroscopy. Chromatography A 1492:106-116.

U.S. Environmental Protection Agency. Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air, Second Edition, Compendium Method TO-13. EPA/625/R-96/010b, January 1999.

Table Appendix C.1. Study GC-TOF-MS PAH and PAC Method Detection Limits (ng filter-1).

Analyte PM* TSP* PUF*

Naphthalene 53.8 23.1 99.6Acenaphthylene 1.17 1.13 1.32Acenaphthene 2.44 12.3 13.5Fluorene 5.81 17.1 11.7Phenanthrene 13.7 35.2 25.2Anthracene 699 3.94 2.09Fluoranthene 5.34 39.9 15.8Pyrene 14.9 31.8 15.6Benzo[c]phenanthrene 2.50 3.82 5.10Benz[a]anthracene 0.65 25.1 15.2Chrysene 1.91 25.9 26.8Benzo[bj]fluoranthene 1.32 29.1 26.8Benzo[k]fluoranthene 0.64 11.0 9.5Benzo[e]pyrene 0.63 14.5 16.5Benzo[a]pyrene 10.58 19.4 4.2Indeno[1,2,3-cd]pyrene 1.28 11.5 13.3Dibenz[a,h]anthracene 7.55 5.11 4.62Benzo[g,h,i]perylene 1.26 15.3 26.11-Methylnaphthalene 7.69 30.2 40.12-Methylnaphthalene 4.55 17.7 23.4C1-Fluorenes 167 6.46 10.2Dibenzothiophene 18.9 2.28 1.974-Methyldibenzothiophene 3.09 1.38 3.582/3-Methyldibenzothiophene 2.77 1.38 3.461-methyldibenzothiophene 2.13 0.881 3.25C1-Phenanthrenes 36.1 23.1 43.8Retene 22.2 1.83 122C1-Fluoranthenes 26.8 18.8 28.9C1-Chrysenes 3.09 8.33 30.0C1-Benzopyrenes 3.10 77.6 64.0C2-Naphthalenes 10.1 44.0 44.8C2-Dibenzothiophenes A 6.41 1.60 8.53C2-Dibenzothiophenes B 17.7 6.11 20.9C2-Phenanthrenes 133 26.4 87.8C2-Fluoranthenes 61.1 17.9 41.8C2-Chrysenes A 11.7 35.9 82.1C2-Chrysenes B 2.46 5.20 11.5C2-Benzopyrenes 2.51 0.939 2.82

*A Study specific MDL was calculated as t0.01,(n-1) × standard deviation of the 28 PM and 16 TSP and PUF/XAD laboratory blank values for each analyte.

Table Appendix C.2. Inorganic MDL and Percent above MDL, by Analyte and Size Fraction.

Analyte Unit PM2.5 MDL* % > MDL PM10-2.5 MDL* % > MDLPM2.5 Mass g m-3 0.12 100 0.16 99Aluminum ng m-3 2.45 100 5.81 100Antimony ng m-3 0.0019 100 0.0033 99Arsenic ng m-3 0.0082 100 0.0055 99Barium ng m-3 0.14 98 0.11 98Beryllium ng m-3 0.0074 38 0.0080 70Bismuth ng m-3 0.0028 91 0.0021 66Cadmium ng m-3 0.0022 97 0.0014 85Calcium ng m-3 13.95 100 16.16 99Cerium ng m-3 0.0028 100 0.0041 100Cesium ng m-3 0.0012 100 0.0008 100Chromium ng m-3 0.16 85 0.18 78Cobalt ng m-3 0.0026 100 0.0208 79Copper ng m-3 0.40 79 0.13 87Iron ng m-3 2.52 100 6.31 99Lanthanum ng m-3 0.0012 100 0.0012 99Lead ng m-3 0.014 100 0.012 95Lithium ng m-3 0.0086 97 0.0170 96Magnesium ng m-3 0.99 100 0.97 100Manganese ng m-3 0.082 100 0.223 98Molybdenum ng m-3 0.0035 100 0.0143 89Neodymium ng m-3 0.0011 100 0.0018 100Nickel ng m-3 0.13 82 0.19 66Niobium ng m-3 0.0019 100 0.0039 97Phosphorus ng m-3 7.91 94 3.36 97Platinum ng m-3 0.0012 13 0.0012 24Potassium ng m-3 1.16 100 1.54 99Praseodymium ng m-3 0.0008 100 0.0006 100Rubidium ng m-3 0.0023 100 0.0124 99Samarium ng m-3 0.0012 98 0.0007 100Selenium ng m-3 0.014 97 0.021 83Silicon ng m-3 33.59 97 50.1 100Sodium ng m-3 1.77 100 0.67 100Strontium ng m-3 0.039 100 0.038 100Sulfur g m-3 0.0010 100 0.0009 100Tantalum ng m-3 0.0008 55 0.0006 91Thallium ng m-3 0.0012 85 0.0003 96Thorium ng m-3 0.0014 100 0.0012 99Tin ng m-3 0.138 77 0.078 54Titanium ng m-3 0.096 100 0.107 100Tungsten ng m-3 0.0063 83 0.0233 62Uranium ng m-3 0.0008 95 0.0004 100Vanadium ng m-3 0.025 100 0.027 100Zinc ng m-3 0.59 100 0.49 92

*A Study specific MDL was calculated for each analyte as 2 times the standard deviation of the field blank concentration.

Table Appendix C.3. Bertha Ganter Fort McKay Site Alberta Ambient Air Quality Objectives (AAAQO) & Alberta Ambient Air Quality Guideline (AAAQG) Exceedances (October 20, 2014 – October 27, 2015).

Analyte Units Hourly Daily # Hourly Exceedances # Daily ExceedancesPM2.5 Mass g m-3 80* 30 101* 11Sulfur Dioxide ppb 172 48 0 0Nitrogen Dioxide ppb 159 N/A 0 N/AAmmonia ppb 2000 N/A 0 N/AHydrogen Sulfide ppb

Sulfide10 3 0 0

*AAAQG

Table Appendix C.4. Ambient PAH Concentrations Collected on PUF/XAD and TSP Samples (ng m-3).

PUF/XAD n Mean Std. Dev. PUF/XAD n Mean Std. Dev.Naphthalene 16 6.163 5.30 Benz[a]anthracene 0 . .Acenaphthylene 14 0.296 0.462 Chrysene 1 0.091 .Acenaphthene 16 0.868 0.844 Benzo[bj]fluoranthene 0 . .Fluorene 17 0.941 0.655 Benzo[k]fluoranthene 0 . .Phenanthrene 17 1.810 1.75 Benzo[e]pyrene 0 . .Anthracene 10 0.070 0.041 Benzo[a]pyrene 2 .023 .006Fluoranthene 11 0.178 0.242 Indeno[1,2,3-cd]pyrene 0 . .Pyrene 13 0.188 0.287 Dibenz[a,h]anthracene 0 . .Benzo[c]phenanthrene 0 - - Benzo[g,h,i]perylene 0 . .

TSP n Mean Std. Dev. TSP n Mean Std. Dev.Naphthalene 1 0.096 - Benz[a]anthracene 1 0.153 -Acenaphthylene 3 0.006 0.003 Chrysene 7 0.308 0.242Acenaphthene 1 0.036 - Benzo[bj]fluoranthene 6 0.215 0.123Fluorene 0 - - Benzo[k]fluoranthene 5 0.073 0.040Phenanthrene 3 0.198 0.089 Benzo[e]pyrene 2 0.203 0.068Anthracene 2 0.043 0.034 Benzo[a]pyrene 2 0.182 0.080Fluoranthene 3 0.147 0.019 Indeno[1,2,3-cd]pyrene 6 0.077 0.037Pyrene 3 0.235 0.103 Dibenz[a,h]anthracene 4 0.025 0.012Benzo[c]phenanthrene 0 - - Benzo[g,h,i]perylene 3 0.115 0.053

Table Appendix C.5. Ambient PAC Concentrations Collected on PUF/XAD and TSP Samples (ng m-3).

PUF n Mean Std. Dev. PM10 n Mean Std. Dev.1-Methylnaphthalene 17 6.314 5.59 C2-Naphthalenes 16 8.094 7.472-Methylnaphthalene 17 4.061 3.54 C2-DBTs A 13 0.315 0.272C1-Fluorenes 17 0.959 0.637 C2-DBTs B 10 0.536 0.483Dibenzothiophene 17 0.350 0.335 C2-Phenanthrenes 16 1.120 0.9814-MethylDBT 13 0.468 0.339 C2-Fluoranthenes 1 0.146 -2/3-MethylDBT 13 0.336 0.259 C2-Chrysenes A 0 - -1-MethylDBT 11 0.327 0.233 C2-Chrysenes B 0 - -C1-Phenanthrenes 17 1.677 1.18 C2-BP/BF marker 0 - -Retene 2 1.758 2.00C1-Fluorenes 6 0.181 0.116C1-Chrysenes 0 - -C1-BP/BF 0 - -  

TSP n Mean Std. Dev. PM2.5 n Mean Std. Dev.1-Methylnaphthalene 3 0.096 0.004 C2-Naphthalenes 3 0.163 0.0322-Methylnaphthalene 1 0.052 - C2-DBTs A 13 0.077 0.111C1-Fluorenes 4 0.044 0.026 C2-DBTs B 10 0.131 0.191Dibenzothiophene 5 0.037 0.036 C2-Phenanthrenes 10 0.884 1.144-MethylDBT 14 0.057 0.087 C2-Fluoranthenes 8 0.344 0.3802/3-MethylDBT 12 0.058 0.080 C2-Chrysenes A 7 0.740 0.6371-MethylDBT 10 0.030 0.038 C2-Chrysenes B 6 0.097 0.087C1-Phenanthrenes 8 0.430 0.492 C2-BP/BF marker 2 0.069 0.088Retene 14 0.430 0.647C1-Fluorenes 7 0.312 0.297C1-Chrysenes 12 0.319 0.346C1-BP/BF 3 0.406 0.079  

Table Appendix C.6. PM10 PAH & PAC Analytical Precision from Replicate Analysis (n = 29).PAH APD§ PAH APD§ C1 PAC APD§ C2 PAC APD§

Naphthalene 17.7% Benz[a]anthracene 14.4% 1-Methylnaphthalene 16.3% C2-Naphthalenes 6.0%Acenaphthylene 48.1% Chrysene 14.8% 2-Methylnaphthalene 9.3% C2-DBTs A 5.6%Acenaphthene 73.4% Benzo[bj]fluoranthene 11.8% C1-Fluorenes 43.2% C2-DBTs B 9.1%Fluorene 5.9% Benzo[k]fluoranthene 29.5% Dibenzothiophene 4.3% C2-Phenanthrenes 5.5%Phenanthrene 26.9% Benzo[e]pyrene 21.4% 4-MethylDBT* 5.0% C2-Fluoranthenes 7.3%Anthracene 10.0% Benzo[a]pyrene 17.5% 2/3-MethylDBT 20.4% C2-Chrysenes A 12.4%Fluoranthene 12.9% Indeno[1,2,3-cd]pyrene 17.7% 1-MethylDBT 19.8% C2-Chrysenes B 20.6%Pyrene 14.0% Dibenz[a,h]anthracene 31.3% C1-Phenanthrenes 23.3% C2-Benzopyrenes 42.6%Benzo[c]phenanthrene 17.7% Benzo[g,h,i]perylene 5.3% Retene 26.6%            C1-Fluorenes 22.5%            C1-Chrysenes 15.7%            C1-Benzopyrenes 28.9%    

§ APD = average percent difference*DBT = dibenzothiophene

Table Appendix C.7. PM2.5 PAH & PAC Analytical Precision from Replicate Analysis (n = 29).PAH APD§ PAH APD C1 PAC APD C2 PAC APD

Naphthalene 25.0% Benz[a]anthracene 13.8% 1-Methylnaphthalene 16.5% C2-Naphthalenes 22.8%Acenaphthylene 29.4% Chrysene 8.8% 2-Methylnaphthalene 24.4% C2-DBTs A 34.3%Acenaphthene 49.4% Benzo[bj]fluoranthene 12.8% C1-Fluorenes 9.6% C2-DBTs B 88.0%Fluorene 183.0% Benzo[k]fluoranthene 30.2% Dibenzothiophene 15.0% C2-Phenanthrenes 24.7%Phenanthrene 19.0% Benzo[e]pyrene 20.0% 4-MethylDBT 6.5% C2-Fluoranthenes 9.4%Anthracene 22.9% Benzo[a]pyrene 26.2% 2/3-MethylDBT 8.7% C2-Chrysenes A 28.8%Fluoranthene 22.0% Indeno[1,2,3-cd]pyrene 18.2% 1-MethylDBT 17.9% C2-Chrysenes B 6.9%Pyrene 19.2% Dibenz[a,h]anthracene 31.2% C1-Phenanthrenes 10.9% C2-Benzopyrenes 7.7%Benzo[c]phenanthrene 22.6% Benzo[g,h,i]perylene 13.7% Retene 16.2%            C1-Fluorenes 13.2%            C1-Chrysenes 20.7%            C1-Benzopyrenes 63.9%    

§ APD = average percent difference*DBT = dibenzothiophene

Table Appendix C.8. PAH and PAC Field Blanks for PM, TSP, and PUF/XAD (ng sample-1).

Analyte PM10 PM2.5 TSP PUF/XADn Mean Std Dev n Mean Std Dev n Mean Std Dev n Mean Std Dev

Naphthalene 15 -0.303 4.50 14 1.66 5.06 3 -1.73 1.59 4 189 118Acenaphthylene 14 5.83 3.12 13 4.63 3.54 2 0.309 0.123 3 10.3 3.99Acenaphthene 4 1.32 1.28 4 2.65 3.34 3 -1.43 4.95 4 36.3 8.39Fluorene 15 78.5 36.6 14 83.3 33.9 3 -2.23 6.13 4 40.5 11.7Phenanthrene 12 50.8 54.6 14 57.0 95.0 3 -5.66 8.97 4 11.8 5.29Anthracene 7 -217 189 6 -56.0 82.0 2 0.251 0.762 2 1.07 0.150Fluoranthene 14 19.0 27.6 14 13.1 18.7 3 -1.57 1.61 4 0.711 0.412Pyrene 15 55.8 39.3 14 57.1 38.0 3 -1.10 1.20 3 -0.020 0.326Benzo[c]phenanthrene 3 1.86 2.16 2 0.631 0.195 2 0.151 0.093 0 - -Benz[a]anthracene 11 6.40 8.60 8 5.79 10.9 2 -0.150 0.154 2 0.113 0.026Chrysene 12 11.4 12.5 13 14.6 29.1 3 -0.751 0.979 2 0.209 0.021Benzo[bj]fluoranthene 4 11.9 8.50 7 7.70 13.6 3 -0.767 1.07 1 0.135 -Benzo[k]fluoranthene 4 5.72 5.40 3 4.39 5.86 2 -0.021 0.869 0 - -Benzo[e]pyrene 6 15.3 13.2 8 8.68 15.6 2 2.92 8.97 1 -0.068 -Benzo[a]pyrene 5 6.01 5.74 5 5.36 13.1 0 - - 0 - -Indeno[1,2,3-cd]pyrene 2 13.8 0.785 2 8.86 6.30 3 -2.36 3.18 1 -0.012 -Dibenz[a,h]anthracene 1 -1.14 - 2 4.65 5.97 2 -0.182 0.034 0 - -Benzo[g,h,i]perylene 5 7.40 7.29 7 5.38 13.6 2 -0.091 0.648 2 0.103 0.0451-Methylnaphthalene 15 6.87 10.1 14 9.64 15.2 4 7.07 13.8 4 388 2222-Methylnaphthalene 15 5.93 7.56 14 5.96 12.7 4 2.66 7.15 4 186 92.6C1-Fluorenes 15 97.4 72.3 14 98.5 71.0 4 -1.01 1.39 4 12.3 3.96Dibenzothiophene 15 5.66 6.05 14 9.68 16.0 4 0.042 0.935 4 2.41 0.6654-Methyldibenzothiophene 15 14.5 7.54 14 16.4 16.4 4 -0.159 0.620 4 0.779 0.4172/3-Methyldibenzothiophene 12 15.8 9.59 13 16.4 15.8 4 0.184 0.301 3 0.483 0.1301-Methyldibenzothiophene 15 21.2 8.77 14 20.9 14.3 3 0.024 0.362 2 0.224 0.096C1-Phenanthrenes 15 128 71.1 14 121 83.8 3 -8.65 8.86 4 7.02 2.51Retene 15 76.6 103 14 59.1 73.8 4 0.510 0.510 2 0.833 0.223C1-Fluoranthenes 15 61.1 60.3 14 72.5 99.5 4 -0.920 1.11 4 4.61 1.66C1-Chrysenes 15 22.5 18.8 14 38.0 79.4 4 -0.726 0.835 4 3.13 2.00C1-Benzopyrenes 15 45.0 58.0 14 53.5 100 2 2.56 7.37 4 8.67 4.48C2-Naphthalenes 15 36.9 27.8 14 50.3 43.8 4 6.52 6.54 4 282 91.6C2-Dibenzothiophenes A 15 32.0 16.7 14 31.8 25.1 4 -0.268 0.859 4 0.623 1.07C2-Dibenzothiophenes B 15 47.7 26.5 14 55.3 64.0 4 0.597 3.11 2 1.06 0.778C2-Phenanthrenes 15 279 179 14 252 201 4 -10.4 5.57 2 5.33 11.2C2-Fluoranthenes 14 214 136 14 169 169 2 -0.808 5.29 3 1.46 1.39C2-Chrysenes A 15 53.8 36.5 14 64.4 112 2 3.86 0.867 1 5.03 -C2-Chrysenes B 10 7.36 2.81 9 9.16 12.9 1 0.773 - 0 - -C2-Benzopyrenes 2 2.62 1.15 1 18.4 - 0 - - 0 - -

Figure Appendix D.1. Comparison of the Dichotomous Sampler and SHARP Instrument PM2.5

Mass at Bertha Ganter Fort McKay Monitoring Site (Oct. 20, 2014 – Oct. 27, 2015).

SHARP Instrument PM2.5 (g m-3)

0 10 20 30 40 50 60 70 80 90 100

Dichotom

ous Sam

pler PM

2.5 (

g m-3

)

0

10

20

30

40

50

60

70

80

90

100

Dichot = (0.988 * SHARP) + 0.617r2 = 0.924p < 0.0001

Appendix Figure D.2. Relative Frequency Histograms of Dichotomous Sampler PM2.5 (a) and PM10-2.5 (b) Mass at Bertha Ganter Fort McKay Monitoring Site (Oct. 20, 2014 – Oct. 27, 2015).

Dichotomous Sampler Fine PM Mass (g m-3)

0 20 40 60 80

Count

0

20

40

60

80(a)

Dichotomous Sampler Coarse PM (g m-3)

0 5 10 15 20 25 30 35 40

Count

0

10

20

30

40

50(b)

Figure Appendix D.3. Time Series of Bertha Gartner Fort McKay PM2.5 Monthly Geometric Mean Mass Concentrations (the Study Period is Shown Inside Blue Box).

Figure Appendix D.4. Relationship Between Hourly Median PM2.5, BC, UVPM and UVPM/BC Ratio at Bertha Ganter Fort McKay During the Study Period (October 2014 – October 2015).

Figure Appendix D.5. Time Series of Hourly PM2.5 Mass, BC, and UVPM at Fort McKay during Wildland Fire Event Impacts.

Figure Appendix D.6. Time Series of Hourly BC, UVPM, and Ammonia at Bertha Ganter Fort McKay during Wildland Fire Event Impacts.

Figure Appendix D.7. Relationship Between Hourly PM2.5 Mass when Concentrations were > 40 g m-3 and Delta-C, Total Reduced Sulfur, and Ammonia at Bertha Ganter-Fort McKay Site.

NOTE: Only non-zero NH3 values plotted and included in equation.

Figure Appendix D.8. Relationship between Hourly Delta-C and PM2.5 Mass during July 3-4, 2015 Wildland Fire Event at Bertha Ganter Fort McKay (n = 35 Hourly Observations).

SHARP PM2.5 (g m-3)

0 100 200 300 400 500

Delta-C

(ng m-3

)

0

5000

10000

15000

20000

25000

30000

Delta-C = (61.16 * PM2.5) - 3318r2 = 0.966p < 0.0001

Figure Appendix D.9. Relationship between Hourly Delta-C and PM2.5 Mass during July 11-12, 2015 Wildland Fire Event at Bertha Ganter Fort McKay (n = 37 Hourly Observations).

SHARP PM2.5 (g m-3)

0 100 200 300 400 500

Delta-C

(ng m-3

)

0

5000

10000

15000

20000

25000

30000

Delta-C = (21.19 * PM2.5) + 441r2 = 0.869p < 0.0001

Figure Appendix D.10. Particle-Vapor Phase Partitioning of PAHs and PACs by Season.

C2-Benzopyrenes

Dibenz[a,h]anthracene

Indeno[1,2,3-cd]pyrene

Benzo[g,h,i]perylene

C1-Benzopyrenes

C2-Chrysenes

Benzo[bj]fluoranthene

Benzo[k]fluoranthene

Benzo[e]pyrene

Benzo[a]pyrene

C1-Chrysenes

C2-Fluoranthenes

Benz[a]anthracene

Chrysene

Retene

C1-Fluoranthenes

C2-Dibenzothiophenes

C2-Phenanthrenes

Fluoranthene

Pyrene

4-Methyldibenzothiophene

2/3-Methyldibenzothiophene

1-methyldibenzothiophene

C1-Phenanthrenes

Dibenzothiophene

C1-Fluorenes

Phenanthrene

Anthracene

Fluorene

C2-Naphthalenes

Acenaphthene

Acenaphthylene

1-Methylnaphthalene

2-Methylnaphthalene

Naphthalene

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Winter mean Summer mean

Fraction of analyte on TSP filter

Figure Appendix D.11. Relative Contributions of Individual PAHs to Total PAHs in TSP + PUF/XAD.

Naphthalene

Acenaphthyle

ne

Acenaphthene

Fluorene

Phenanthrene

Anthracene

FluoranthenePyre

ne

Benzo(c)

perylene

Benz(a)anthrace

ne

Chrysene

Benzo(bj)fl

uoranthene

Benzo(k)

fluoranthene

Benzo(e)pyre

ne

Benzo(a)pyre

ne

Indenopyrene

Dibenz(a,h)anthrace

ne

Benzo(ghi)p

erylene

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Summer Winter

Frac

tion

of to

tal P

AH

Figure Appendix D.12. Relative Contribution of Individual PACs to Total PACs in TSP + PUF/XAD

Figure Appendix D.13. Comparison of Ambient Particulate Phase PAHs and PACs in TSP versus PM10.

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 20

0.5

1

1.5

2

ChryseneBenzo(e)pyreneBenzo[ghi]peryleneC1-ChrysenesC2-Chrysenes

PM10, ng/m3

TSP,

ng/

m3

Figure Appendix D.14. Box and Whisker Plots for PM2.5 (a) and PM10-2.5 (b) Trace Elements (ng m-3).

(a)

(b)

Figure Appendix D.15. PM2.5 to PM10-2.5 Ratios for Mass and Trace Elements (Based on Study Means).

Figure Appendix D.16. 24-hour Average PM2.5 and PM10-2.5 Mass (g m-3).

Figure Appendix D.17. 24-hour Average PM2.5 and PM10-2.5 Sulfur Concentrations.

Figure Appendix D.18. Daily Average Concentrations of Aluminum, Iron and Potassium (ng m-3).

Figure Appendix D.19. Daily Average Concentrations of Cadmium, Lead and Molybdenum (ng m-3).

Figure Appendix D.20. SWIM Model Spatial Source Probability for NH3.