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Characterization of Natural and Affected Environments
Deposition and source identification of nitrogen heterocyclic polycyclic aromatic compounds in snow, sediment, and air samples from the Athabasca Oil Sands Region Leah Chibwe, Carlos A Manzano, Derek Muir, Beau Atkinson, Jane L. Kirk, Christopher H. Marvin, Xiaowa Wang, Camilla Teixeira, Dayue Shang, Tom Harner, and Amila O. De Silva Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b06175 • Publication Date (Web): 11 Feb 2019 Downloaded from http://pubs.acs.org on February 17, 2019
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Deposition and source identification of nitrogen heterocyclic polycyclic aromatic
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compounds in snow, sediment, and air samples from the Athabasca Oil Sands Region
3 4
Leah Chibwe,*1 Carlos A. Manzano,2,3 Derek Muir,1 Beau Atkinson,1 Jane L. Kirk,1 Christopher
5
H. Marvin,1 Xiaowa Wang,1 Camilla Teixeira,1 Dayue Shang,4 Tom Harner,5 Amila O. De Silva1
6 7
1Aquatic
8
ON
9
2Center
for Environmental Science, Faculty of Science, University of Chile, Santiago, Chile
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3School
of Public Health, San Diego State University, San Diego, CA
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4Pacific
and Yukon Laboratory for Environmental Testing, Environment & Climate Change
12
Canada, North Vancouver, BC
13 14
5Air
Contaminants Research Division, Environment & Climate Change Canada, Burlington,
Quality Processes Research Division, Environment & Climate Change Canada, Toronto,
ON
15 16
Corresponding author:
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*Environment and Climate Change Canada, 867 Lakeshore Rd, Room L650A, Burlington ON
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L7S 1A1, Phone: 905-336-4541
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Email:
[email protected] 20
ABSTRACT
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Polycyclic aromatic compounds (PACs) can have multiple sources in the Athabasca Oil
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Sands Region (AOSR). The current study was designed to identify and explore the potential of 1 ACS Paragon Plus Environment
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nitrogen heterocyclic PACs (NPACs) as source indicators in snowpack, lake sediment and
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passive air samples from the AOSR during 2014-2015. Source samples including petroleum coke
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(petcoke), haul road dust and unprocessed oil sands were also analyzed. Samples were analyzed
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using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry and
27
liquid chromatography-high resolution Orbitrap mass spectrometry. Over 200 NPACs were
28
identified and classified into at least 24 isomer groups, including alkylated carbazoles,
29
benzocarbazoles and indenoquinolines. Levels of NPACs in environmental samples decreased
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with distance from the main developments, and with increasing depth in lake sediments, but were
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detected within 50 km from the major developments. The composition profiles of several NPAC
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isomer classes, such as dimethylcarbazoles, showed that petcoke had a distinct distribution of
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NPACs compared to the haul road dust and unprocessed oil sands ores, and was the most similar
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source material to near-field environmental samples. These results suggest that petcoke is a
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major contributing source for the identified NPACs, and that these compounds have the potential
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to be used as source indicators for future research in the AOSR.
37 38
1. INTRODUCTION
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The Athabasca Oil Sands Region (AOSR) deposits located in Northern Alberta, Canada, are
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considered one of the world’s largest oil reserves. The oil sands contain a mixture of naturally
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occurring sands, water and approximately 4-6 % bitumen.1, 2 Bitumen is separated from this
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mixture using steam and undergoes upgrading to produce light crude oils.3 Petcoke, a
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carbonaceous by-product of the upgrading process, is often stored in stockpiles within the
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AOSR.4 According to a report by the Canadian Association of Petroleum Producers, 2.4 million
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barrels per day of these oil reserves were recovered in 2016 with a projected increase to 4.0
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million barrels per day by 2025.3 This presents on-going environmental concerns such as the
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release of airborne pollutants, including polycyclic aromatic compounds (PACs), associated with
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the mining and upgrading processes in the AOSR.5, 6
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PACs are persistent organic contaminants, composed of fused-benzene rings, and many
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are linked to carcinogenic and/or mutagenic effects.7-9 PACs have been detected in sediments of
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lakes,6, 10 air particulate matter,11-14 moss,1 lichen,15, 16 and snow,1, 12, 13 both near and far from
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upgrading facilities within the AOSR. Several sources of PACs have been suggested, including
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bitumen upgrader emissions, tailing sands, fugitive dust, biomass burning, oil sands ore, and
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petroleum coke (petcoke).1, 2, 11, 13, 17-20 However, since PACs can have both natural and
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anthropogenic sources, more knowledge is needed to fully understand and characterize the major
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industrial sources and environmental burden of PACs in the AOSR.
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The focus in understanding PAC distributions and sources in the AOSR has mainly been on
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unsubstituted (unPACs), selected groups of alkylated PACs (aPACs) and dibenzothiophenes
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(DBTs), even though it is well-known that PACs exist in the environment as complex mixtures.
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Heterocyclic PACs, containing an oxygen, nitrogen or sulphur atom within a ring, comprise one
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of the least studied groups of PACs.21 There are few authentic standards available, and the high
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number of potential isomers present challenges in the separation, identification and quantitation
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of these more polar PAC analogue compounds in environmental samples. Several studies suggest
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that these heterocyclic compounds can be just as prevalent as the most routinely monitored PACs
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in the environment.13, 22-28 N-containing heterocyclic PACs (NPACs) have been detected in air
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particulate and sediment samples,23 and in soils associated with coal production.28 Specific to the
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AOSR, Manzano et al. tentatively identified over 250 chromatographic features, mainly
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associated to S-containing heterocyclic PACs (SPACs) in snowpack, air particulate matter and
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sediment samples.13 Although there is also paucity in toxicity data for these heterocyclic PACs,
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several have been shown to be toxic in embryonic zebrafish, marine and land invertebrates, and
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in plant assays.29-33 Effect threshold concentrations in these assays have been observed to be
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comparable, if not lower, than the corresponding unsubstituted PAC homologs.29-33 Neglecting to
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address the contribution of these compounds may greatly underrepresent the overall impact of
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PACs in monitoring assessments in the AOSR.
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The objectives of this study were to for the first time (1) identify NPACs in snow, passive air
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and sediment samples from the AOSR, (2) to characterize the distribution of these compounds in
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6 source materials (a road dust, oil sands ores, and petcoke samples), and (3) use the profiles of
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the source materials for source apportionment, using comprehensive two-dimensional gas
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chromatography mass spectrometry (GC×GC/ToF-MS) and liquid chromatography-high mass
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resolution (Orbitrap) spectrometry (LC-HRMS). We hypothesized that NPACs are enriched
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within AOSR source materials, thus providing unique source signatures.
82 83 84
2. METHODS 2.1. Chemicals and Materials. The following authentic standards for NPACs: carbazole,
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acridine, phenanthridine, 8,10-dimethylbenzo[a]acridine, benz[a]acridine, 3,6-
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dimethylcarbazole, benzocarbazole, 7,8-benzo[h]quinolone, 2,4-dimethylbenzo[h]quinolone,
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benz[c]acridine, 1,5-dimethylcarbazole, 4H-benzo[def]carbazole, and dibenzo[a,j]acridine, were
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purchased from Cambridge Isotope Labs (Andover, MA) and Sigma Aldrich (Oakville, CA).
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2.2. Snow, sediment, air, and source materials. Details on the collection, locations and
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procedures for the environmental samples have been extensively described previously,12, 13 and
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are provided in further detail in the Supporting Information. Briefly, the sampling information is
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summarized as follows:
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Snow. The snowpack samples used in this study were collected as part of the Joint Canada-
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Alberta Oil Sands Monitoring (JOSM) program in the Regional Municipality of Wood Buffalo,
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northern Alberta, at varying distances from a widely studied site (AR6) located near oil sands
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upgrading operations (Figure S1).12, 34, 35 Under JOSM, the unPAC and aPAC concentrations
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from 2011-2014 have also been reported.12 In this study, 21 samples from 2014 collected
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between late February and early March, up to 80 km from AR6 were selected for NPAC
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analysis.
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Briefly, melted snow was first filtered through a glass fibre filter (GF/F), then passed through
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a column packed with a XAD-2 resin. Filters were spiked with labeled standards, and the
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particulate matter on filters were then extracted using pressurized liquid extraction (PLE)
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(Dionex ASE 350, Thermo Fisher Scientific) with hexane-acetone (1:1), followed by
104
dichloromethane (DCM). The XAD-2 resin was extracted on an elution column with acetone and
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DCM. The PLE and XAD extracts were both back extracted with 3% sodium chloride solution to
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remove acetone before drying with sodium sulphate. They were then concentrated, solvent
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exchanged into cyclohexane, and combined for the total NPACs from particle and the dissolved
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fractions of the snow samples. The combined extract was then fractionated using silica gel
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columns that were eluted with hexane followed by benzene to elute the aromatic fraction of
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interest.
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Passive air samples. The passive air samples were collected in 2015, also as part of the
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JOSM monitoring program.13, 14 In brief, polyurethane foam (PUF) disks were deployed at 5
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sites (AMS 5, 13, 9, 6 and 14) in the AOSR (Figure S1). The PUF disks were spiked with labeled
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standards and extracted by PLE with two cycles of petroleum ether and acetone (75:25, v/v). The
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extracts were then purified using silica gel columns (Agilent Technologies) with DCM as the
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eluent. The extracts were finally concentrated under a steady stream of nitrogen prior to analysis.
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Sediment cores. A sediment core was collected in 2015 from Lake NE20 located at
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57.125 oN, 111.56 oW, near upgrading and mining operations (Figure S1). This lake has an area
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of 0.05 km2 and catchment of 2.1 km2. The sediment core was sampled and dated using isotopes
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210-Pb and 137-Cs as described by Kurek et al.6
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Source materials. The source materials investigated in this study were haul road dust,
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delayed petcoke, and oil sands ores. The representative haul road dust source material was
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prepared using composite roof and surface dust collected off mining trucks and other vehicles
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carrying bitumen ore within the mining operations, since dust from haul and transport roads has
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previously been identified as a major source of air pollution in other mining areas.36, 37
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Delayed petcoke and oil sands bitumen ore samples were obtained from two companies
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operating within the AOSR with the cooperation of the Canadian Oil Sands Innovation Alliance.
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In addition, samples of petcoke collected in the Anzac area (about 30 km south of Fort
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McMurray, AB), and of delayed and fluidized petcoke, were provided by Yifeng Zhang and
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Jonathan Martin (University of Alberta/Stockholm University). These samples have been
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previously characterized for a less extensive suit of unPACs, aPACs and SPACs.1, 13 The
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fluidized petcoke sample was analyzed and had negligible levels of NPACs, and was excluded
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from analysis in this study. This result was consistent with previous results for unPACs, aPACs
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and SPACs in fluidized petcoke.1, 13 The differences in delayed and fluidized petcoke stem from
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differences in processing methods. While both types are derived from bitumen containing high
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sulfur content, delayed petcoke is produced at lower temperatures often resulting in higher levels
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of volatiles than fluidized petcoke.38
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Sediments and source materials were extracted as described by Shang et al.39 In brief,
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about 10 g freeze dried subsample was weighed into a polypropylene centrifuge tube. Mass
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labeled standards of unPACs, about 5 g sodium sulphate, 1 g Florisil, and 15 mL of DCM were
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also added to the tube. The tube was agitated on a shaker for 10 min, centrifuged, and the solid
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sample cake was re-extracted with 7 mL of fresh DCM. The combined supernatant was made up
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to a volume of 20 mL with DCM. Of this extract, 1 mL was passed through a silica gel column,
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and eluted with 10 mL of DCM. The extract was then concentrated to 1 mL for analysis.
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2.3. GC×GC-TOF-MS Analysis. All extracts were analyzed using a GC×GC/ToF-MS
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Pegasus 4D (LECO, St Joseph, MI) instrument. The instrument consisted of an Agilent 7890B
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gas chromatograph (Palo Alto, CA) with a consumable-free modulator operated at -80 °C. The
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columns used were the ionic-liquid SLB®-IL60 (20 m × 0.18 mm × 0.14 μm; Sigma Aldrich) and
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Rxi-17 column (1.2 m × 0.10 mm × 0.10 μm; Restek) in the first and second dimension,
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respectively. Details on the oven temperature methods are provided in the Supporting
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Information (Table S2).40 Data processing was performed using the LECO ChromaToF v.4.50.8
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software.
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The tentative identification of unknown NPACs features followed a similar approach
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used previously in the case of SPACs in AOSR samples, using the NIST 11 EI mass spectral
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library and order in elution profiles of peaks in the 2D chromatogram.13 Isomers were
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additionally identified using retention indexes (RI) in the first dimension, determined from the
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compounds: fluorene (RI = 200), phenanthrene (RI = 300), chrysene (RI = 400), benzo[a]pyrene
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(RI = 450) and benzo[ghi]perylene (RI = 500).
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The GC×GC/ToF-MS was calibrated using 13 NPAC standards ranging from 0.5 to 2000
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pg µL-1 (R2 > 0.99). The average response factors (ARF) of the authentic standards were
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determined using a 10-point calibration curve, relative to the internal standard, chrysene-d12,
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which was common to all samples. The %RSD for the ARFs for the authentic standards was
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between 8.1 and 20.6 % (Table S3). The ARFs represent the ratio between the concentrations of
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a compound, and the response of the detector to that compound, over all concentration levels
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within a calibration.41 The ARFs for the authentic standards were between 0.38 and 2.61, lowest
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for the high MW and later eluting compounds (Table S3). Because a large proportion of the
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identified NPAC features lack authentic standards, it is challenging to determine a response
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factor for each tentatively identified feature. Therefore, a composite response factor determined
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from the average ARFs of the 13 NPAC standards was used to estimate concentrations for the
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243 identified NPAC features.
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Field, method and solvent (toluene) blanks, as well as calibration check standards for
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every set of 8 samples were used for quality assurance and control, and also to test for carry over
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during analysis.
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2.4. LC-HRMS analysis. The LC-HRMS analysis was performed on a Vanquish
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UHPLC coupled to a Q Exactive Focus Orbitrap MS (Thermo Fisher Scientific).
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Chromatographic separation was performed using a Poroshell 120, EC-C18 column (3.0 x 100
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mm x 2.7 µm particle size, Agilent Technologies). The mobile phase consisted of a gradient
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elution using water (A) and methanol (B). The heated electrospray ionization (HESI-II) source
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was operated in both positive and negative ionization modes, and source conditions were
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optimized using the NPAC authentic standards and were: sheath gas flow rate, 20 arbitrary units
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(a.u.); auxiliary gas, 5 a.u.; auxiliary temperature, 300 °C; and capillary temperature, 300 °C.
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The ESI-QTOF-MS was operated in full scan data-dependent MS2 (MS/dd-ms2) discovery mode
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and stepwise dd-ms2 fragmentation was conducted at collision energies: 20, 30 and 50 eV. Mass
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calibration was performed using Pierce® LTQ Velos ESI positive and negative ion calibration
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solutions (Thermo Fisher Scientific).
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For the identification of unknowns, the XCalibur and Compound Discoverer 2.0 (Thermo
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Fisher Scientific) software were used. Filters were applied to the Compound Discoverer to
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process the data, including signal to noise (S/N) ratio greater than 5, mass tolerance of 5 ppm,
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and a minimum ratio between samples and blanks of 5.
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2.5 Data analysis. Principal component analysis (PCA) was used as an exploratory tool to
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classify the environmental and source samples based on their NPACs profiles. PCA was
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performed using the composition fraction (concentration of compound relative to the total
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NPACs). The data was log transformed and standardized prior to PCA analysis. A one-way
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analysis of variance (ANOVA) on Ranks non-parametric test with Tukey’s honestly significant
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differences (HSD) post hoc test was used to determine significant differences in estimated NPAC
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concentrations between the different source materials. All analyses were performed using
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SigmaPlot version 14 (Systat Software Inc).
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3. RESULTS AND DISCUSSION 3.1 Identification and characterization of NPACs in Environmental Samples. The snow
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sample, closest to the main upgrading areas in the AOSR (site AR6) was used as reference to
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identify NPACs.5, 12, 13 The column combination with an ionic-liquid stationary phase in
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GC×GC/ToF-MS was effective in separating the NPACs from other components in the samples,
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including SPACs (Figure S2).42 In total, 243 individual features, characterized into 24 isomer 9 ACS Paragon Plus Environment
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classes, were identified based on the NIST 11 mass spectral similarity matching and elution
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profiles in the 2D chromatogram for a given isomer class (Supporting Information S1, Figure
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S3). Classes were assigned names if the isomers had a >80 % average mass spectral similarity
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match, but otherwise were designated as “unknown” (U). RIs in addition to the elution profiles
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were used to identify isomers across samples and were useful in identifying compounds in
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samples that did not contain all isomers for a given class. The average RSD for RIs across all
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samples was 0.1 % (range between 0 and 0.4 %) (Supporting Information S1).
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The high mass resolution capability of LC-HRMS was used as a supplementary technique
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to confirm features. Low NIST mass spectral matches in GC×GC/ToF-MS can occur for a
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number of reasons; the mass spectra for the given compound could be absent in the library or the
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unknown peak could have low S/N values insufficient to obtain a good library match. For
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example, in GC×GC/ToF-MS, a group of ordered isomers with molecular weight (MW) 237
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were matched by the NIST library as features corresponding to phenylthio-isoquinolines,
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C15H11NS (66% NIST score), and isopropyl acridones, C16H15NO (75% NIST score). However,
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given these low mass spectral similarity scores, other features corresponding to formulas
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C14H11N3O, C15H15N3, C15H11NO2 and C16H18N2 were also suggested. In LC-HRMS, peaks
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corresponding to MW 237, and with ring double bond equivalents (RDBEs) characteristic of
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PACs, were identified as C17H19N (3.4 ppm, RDBE 9), C15H11NS (-1.11 ppm, RDBE 11), and
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C16H15NO (2.8 ppm, RDBE 10) (Supporting Information S1). While these LC-HRMS results
224
also suggested the presence of additional PAC-related compounds, the technique allowed for the
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elimination of the other suggested formulas by the NIST library in GC×GC/ToF-MS, and an
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improved characterization of probable structural features. Additionally, dd-ms2 experiments,
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particularly in ESI positive mode, provided further structural information on NPACs. Methylated
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NPACs were distinguished by the initial loss of m/z 15 (-CH3), followed by a loss of m/z 28/27
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(-H2CN) (Figure S4). However, the loss of the m/z 28/27 fragment was dependent on the number
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of methyl-groups, in which case, multiple –CH3 losses were observed. For non-alkylated
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NPACs, generally, the initial main fragment loss corresponded to the m/z 28 ion (-H2CN). These
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fragmentation pathways have been previously observed for NPACs.28, 43
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The Kendrick Mass Defect plot (KMD) from LC-HRMS analysis was used to distinguish
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the unknown features of the same homologous series in the reference snow sample.44 The
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abundances were normalized to the total areas of detected peaks in the sample. The LC-HRMS
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results were in general agreement with GC×GC/ToF-MS in that the most abundant isomer
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classes in the snow reference sample were isomer classes: c2-carbazoles (c2-Car), c1-carbazoles
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(c1-Car), benzocarbazoles (BCar), indenoquinolines (InQ), and unknown 231 (U231)
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(Supporting Information S1, Table S4). These are labelled A-E respectively, in the mass defect
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plots (Figure 1). Additionally, the presence of other homologous series, separated by -CH2,
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observed in the KMD plots from the LC-HRMS data suggested other hetero-containing PACs,
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which could include additional NPACs as well as nitro- and oxy-PACs (Figure 1). It is likely that
243
these compounds were not detected or chromatographically separated with the current
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GC×GC/ToF-MS conditions, but were able to be detected with the high mass resolution
245
capabilities of the LC-HRMS. Aside from a study by Manzano et al. which identified 259
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SPACs in environmental samples in the AOSR,13 monitoring efforts in the AOSR are focused on
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unPACs, aPACs and several DBTs. Combined with the results of this study, there is evidence
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that at least 500 heterocyclic PACs are present in environmental samples in the AOSR along
249
with the routinely studied PACs.
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3.2 Snow, Sediment and Passive Air Samples. The ΣNPACs in snowpack samples were
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between 0.311 and 10,100 pg L-1, generally decreasing with distance from AR6 (Table S5). The
252
concentrations of NPACs were substantially lower than ΣunPACs and ΣaPACs concentrations,
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which have been previously determined to be between 28,800 and 36.8x106 pg L-1, and 111,000
254
and 252x106 pg L-1, respectively.12 However, for many of these compounds, in the absence of
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toxicity data and their interactions in mixtures, further work is needed to discern the
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environmental relevance of these levels.
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We evaluated NPACs in Lake NE20 sediments which is 12 km from AR6, 7 and 9 km
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from a Syncrude coke storage and upgrader stack, respectively (Figure S1, Table S1).6, 45
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Maximum estimated ΣNPACs were found in the most recent horizons dated post ~2000 (2,910-
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49,600 pg g-1 dry wt and lowest in the deep sediments, dated pre-1970 (i.e., pre-development)
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(817-1,910 pg g-1 dry wt) (Figure 2, Table S6). The high levels of NPACs in the most recent
262
horizons confirm results from studies that have shown an increasing trend in PAC concentrations
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from the mid-20th century to modern times, in sediment cores from lakes near upgrading and
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mining facilities in the AOSR.6 High molecular weight unPACs and aPACs were shown to
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dominate the top sections of a sediment core from lake NE20 collected in 2011.3,45 The heavily
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contaminated sections of the sediment core were enriched with isomer classes: U231, c2-Car,
267
BCar, c1-Car, InQ and carbazole (Car) (Table S7).
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The estimated ΣNPACs in the passive air samples ranged between 0.01 and 0.27 pg m-3
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(Table S8). For comparison, Jariyasopit et al. determined the ΣunPAC, ΣaPACs and
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ΣNitro+Oxy-PACs in the same passive air samples to be between 2,110 and 6,750 pg m-3,
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11,000 and 51,500 pg m-3, and 230 and 770 pg m-3, respectively (Table S8).14 The PUF passive
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air samples were enriched in the lower molecular weight isomer classes, particularly carbazole,
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and isomer classes c1-Car, c2-Car and c3-Car (Table S7). This observation is consistent with
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results that show that these samplers collect both ambient gas- and particle associated
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compounds but not larger particles (i.e. > 10 µm) that are subject to near-source deposition from
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air.14 The relationship between ΣNPAC concentrations and distance from AR6, a widely
277 278
studied site near main developments in the AOSR, was explored. In addition, the geographical
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coordinates for each snowpack site were used to determine the distance to the nearest source
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(e.g., coke storage, mine, stack) (Table S1), as multiple oil sands developments spatially exist
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within the AOSR and likely contribute differently to NPAC emissions.46 For the snowpack
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samples, an exponential decay function relationship of the form, f = ae (-bx), where f is the natural
283
logarithm transformed concentration and x is the distance (km) from AR6 was assumed.
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ΣNPACs declined exponentially with increasing distance from AR6, with a decay constant of
285
0.027 (R2 = 0.70, p < 0.0001) (Figure 3A). This decay constant is lower than what has been
286
previously reported for unPACs and aPACs (0.069-0.766 km-1),5, 12, 17 and for SPACs (1.14 km-
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1),13
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AR6 as observed for unPACs and aPACs. The exponential relationship with distance from the
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nearest source similarly showed a decline in NPACs with increasing distance, but a higher decay
290
constant of 0.049 suggesting more rapid concentration gradient concentrated around other point
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sources beyond AR6 (R2 = 0.68, p < 0.0001) (Figure 3A).
suggesting a more gradual concentration gradient as opposed to highly concentrated around
292
In the passive air samples, ΣNPACs were highest at site AMS 5, which is near, AR6 and
293
at site AMS 9, which is 20 km from AR6 but within 10 km of two mines (Figure 3B, Table S8).
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The lowest concentrations of ΣNPACs were at residential/recreational sites AMS 6 and AMS 14.
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samples, with increasing distance from the main developments in the AOSR.11-13 The elevated
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levels confirm that NPACs, like other PACs, largely associate with sources near bitumen mining
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and processing sites.
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3.3. Distinguishing between source materials. The source materials investigated in this
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study were delayed petcoke, oil sands ore, and road haul dust. The differences in estimated
301
concentrations of NPAC isomers between sources samples were statistically significant
302
(P 0.5) (Figure S5).
304
Generally, the levels of NPACs between petcoke and the oil sands ores were comparable within
305
a company (i.e., petcoke 1 and oil sands ore 1 are from company 1). The estimated
306
concentrations in the road dust source material were comparable to those in the petcoke 2 and oil
307
sands ore 2 samples.
308
To study the distribution of the 24 NPAC isomer classes between the source materials,
309
the composition fraction (ratio of concentration of class to total NPACs) was determined (Figure
310
S6, Table S9). The most abundant isomer classes in the petcoke samples by percent composition
311
were: U231 (16-21%), InQ (5.2-17%), BCar (12-23%), c2-Car (12-23%), c1-Car (9.7-19%) and
312
Car (5.4-19%). Among the oil sands ore samples, the most abundant classes were: U223 (27-
313
28%), c3-Car (19-32%), U237A (8.5-12%), c2-Car (8.2-13%), InQ (6.5-9.7%) and U259 (7.6-
314
9.4%). The most abundant classes in the road dust sample were: c3-Car (31%), U223 (20%), and
315
c2-Car (18%). An important distinction between the source materials was that carbazole
316
(confirmed with an authentic standard) represented 5.4 – 19.3 % of total NPACs in the petcokes,
317
whereas in the oil sands ores and haul road dust it had negligible levels between 0 – 0.63%
318
composition (Table S9). It is likely that carbazole is one of the volatiles produced during bitumen
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319
upgrading. Since petcoke is a by-product of bitumen upgrading, carbazole potentially associates
320
more with it than with the oil sands ores. Although carbazole can have both natural and
321
anthropogenic origins, it is most often linked to the latter when found in the environment.47-52
322
Carbazole has been associated with thermal processes, including as a product from coking, oil
323
refining and the incineration of industrial wastes.47-52 The results of the current study suggest that
324
carbazole has the potential to be used as a chemical marker to distinguish between petcoke and
325
oil sands sources, just as DBTs, phenanthrenes and fluorenes are established chemical markers of
326
oil for bitumen, and coke combustion sources, respectively.5, 53, 54
327
Generally, the distribution profiles of the NPAC isomer classes revealed differences
328
between the source materials, suggesting they could be used to provide signatures required for
329
source apportionment of PACs in environmental samples. The availability and chemical profiling
330
of source materials related to industrial activities in the AOSR is beneficial in elucidating the
331
contributions of contaminants resulting from emissions, especially when multiple natural and
332
anthropogenic sources exist, as is the case for PACs.1, 5, 13, 16, 46
333
3.4. Comparison of Source Materials to Environmental Samples. To compare NPAC
334
distributions between the source materials and environmental samples, the composition fractions
335
of each isomer class were evaluated. Visually, there was similarity in profiles between the
336
petcoke source materials and, especially, the near-field snowpack and sediment environmental
337
samples (Figure S6). To further explore these distributions, we considered the patterns of
338
individual carbazole-related features, which included Car, the alkylated-carbazoles, and the
339
benzocarbazoles (Figure 4).
340 341
The first subset of classes (I), comprising the lower MW carbazole and the c1-Cars, were minimally present in the oil sands samples but enriched in the petcoke, road dust, and
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342
environmental samples. This is in contrast to a previous study, that observed an enrichment of
343
lower MW (and more volatile) alkylated PACs in oil sands ore as opposed to petcoke samples.14
344
However, similarly to the aforementioned study,14 the lower MW aPACs like the lower MW
345
NPACs were predominant in the passive air samples, as well as in the snowpack and sediment
346
samples. The predominance of lower MW and usually more volatile PACs, in snow particulate
347
matter has been shown to be typical for compounds stemming from combustion sources.5
348
Furthermore, the profiles of subset class I was similar between the petcoke and the
349
environmental samples, suggesting petcoke as a likely source for these features.
350
The second and third subsets of classes (II, III), comprising isomer classes of c2-Car and
351
c3-Car, showed some distinction between the petcoke (specifically petcokes #1 and #2), oil
352
sands ores and road dust source materials. The isomers in class III were minimally present in
353
petcoke #3, not allowing for comparison with the other source materials. However, the
354
distribution of classes II and III in the snowpack and sediment samples was more similar to the
355
petcoke samples (Figure 4). The last subset of classes (IV), comprising the higher MW
356
compounds, BCar and phenylcarbazoles (PhCar), would be expected to be less volatile than the
357
other carbazoles and primarily exist in the particle phase. These later eluting compounds (IV)
358
were minimally detected in the oil sands ores and road dust source materials, but were more
359
abundant in the petcoke, snowpack and top sediment cores. The distribution profiles of this class
360
were similar between petcoke and the aforementioned environmental samples, suggesting a
361
petcoke influence.
362
The NPAC compositions between the source materials and environmental samples were
363
evaluated by PCA, using features from the most abundant isomer classes in each source material
364
(Car, c1-Car, c2-Car, c3-Car, BCar, U223, U237A and InQ) (133 of the 243 identified features).
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365
The first 2 principal components (PC1, PC2) accounted for 48.5% of the total variance (Figure 5,
366
S7), while up to 10 PCs accounted for 80.6% (Table S10). The PCA component plot for PC1 vs
367
PC2 showed that the snowpack samples within 50 km of AR6, the top sections of the sediment
368
cores (dated post ~2000), and the petcoke samples tended to group together, suggesting influence
369
from petcokes (Figure 5A, S7). The snowpack samples further away from AR6 (> 50 km), and
370
the sediment cores at deeper depths (dated pre ~1960), and the passive air samples, including
371
AMS 5 which is near main developments, mostly clustered separately together. This could
372
indicate the influence of other sources, especially at distal snowpack sites, the influence of a
373
mixture of sources, and/or be representative of a background NPAC signal.
374
The distinction between source materials was also evident as the petcoke samples
375
grouped together and the oil sands samples clustered together, suggesting similarities in physical
376
characteristics as well as with interactions with NPACs (Figure 5A). However, the road dust
377
sample was isolated, indicating it was compositionally different from the other source materials.
378
Comparison of PC1 and the third principal component (PC3) also showed isolation of the road
379
dust sample from the other source materials (Figure 5B). Since the road dust source material was
380
representative of fugitive dust collected off moving vehicles and surfaces in the AOSR, it is
381
likely that there is combined influence from vehicle emissions, combustion and other industrial
382
processes. Additionally, PC1 vs PC3 showed a clustering of the petcokes and oil sands ore
383
source materials and near-field snowpack and sediment samples, suggesting contribution from
384
both petcoke and oil sands ores in the near-field samples (Figure 5B). Using chemical profiling
385
of unPACs, aPACs, oxy- and nitro-PACs, and energy dispersive X-ray spectroscopy of source
386
materials and passive air samples, a recent study observed combined contribution from both
387
petcoke and oil sands ore in passive air samples near mining sites.14
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388
Attributing the sources of PACs in the AOSR is an on-going challenge for a number of
389
reasons; multiple anthropogenic sources, many usually in close proximity to each other, have to
390
be considered. Moreover, PACs interactions with different materials are influenced by their
391
physicochemical properties, and may be greatly impacted by degradation and transformation
392
processes in the environment. The general consensus from multiple studies is that there is a
393
substantial contribution of PACs as a result of mining and upgrading activities, 1, 2, 10, 13-16, 46, 54, 55
394
and consequently that the accurate understanding of sources is necessary to determine the
395
environmental burden of PACs in the AOSR.
396
Petcoke has been suggested as a source for PACs in environmental sources in the AOSR.
397
Manzano et al. 13 identified 259 SPACs and observed that relative distributions of these
398
compounds were similar between delayed petcoke and snow samples less than 30 km from main
399
development areas, as well as near-field sediment and air samples. Priority unPAC and aPAC
400
distributions combined with chemical mass balance (CMB) modelling were evaluated in several
401
source materials (exposed bitumen sample, oil sands ore, fine tailings, delayed and fluid petcoke
402
samples), moss and peat ore samples from the AOSR by Zhang et. al.1 Results from the study
403
showed similarities in PAC profiles between delayed petcoke and moss samples, confirming
404
petcoke as a major source of PACs at near-field sites.1
405
Implications and Limitations. In the current study, 243 non-routinely analyzed NPACs
406
were identified in environmental samples in the AOSR. Together with the study by Manzano et
407
al.,13 there are over 500 N- and S-PACs present in the AOSR and not monitored. This could
408
underestimate the PAC burden to the surrounding environment from industrial and mining
409
activities associated with the AOSR. Moreover, the chemical distribution of these compounds in
410
several source materials showed that they provided unique signatures, from which we were able
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411
to identify petcoke as a major source for these compounds in the AOSR. One of the limitations is
412
that many of the identified heterocyclic PACs lack authentic standards, thus it can be difficult to
413
accurately quantify their contribution, or evaluate their toxicity and bioavailability in the
414
environment. Further work is needed to fully characterize hetero-PACs in the environmental
415
samples from the AOSR. Additionally, LC-HRMS is a promising approach for identifying these
416
classes of compounds in environmental media.
417 418
Supporting Information
419
Sampling and source sites; GC×GC/ToF-MS chromatogram of c3-Carbazoles; First (1tR) and
420
second (2tR) dimension time plots of isomer classes; MS/MS fragmentation patterns for NPACs;
421
Boxplot of log ∑NPAC concentrations between source materials; Log composition fraction of
422
isomer classes; Vector loadings plot NPAC isomers classes in source materials; Table of distance
423
of sites to nearest source in the AOSR; GC×GC/ToF-MS oven temperature program; Correlation
424
co-efficients, response factors and retention indexes of 13 NPAC authentic standards; Percent
425
composition of NPAC isomer classes in snowpack samples; Estimated ΣNPACs concentrations
426
in snowpack; Percent composition of NPAC isomer classes in sediment cores and passive air
427
samples; Estimated ΣNPACs concentrations in passive air samples; Percent composition of
428
NPAC isomer classes in source materials; Principal components of NPACs.
429
Acknowledgements
430
We would like to thank the ECCC Air Quality and Research Division laboratory (Ottawa,
431
ON) for the silica gel cleanup and GC-MS analysis of PACs in the 2014 snow samples, the
432
ECCC Pacific and Yukon Laboratory for Environmental Testing (Vancouver, BC) for the
433
extraction of the source materials and sediment samples, and Fan Yang (ECCC, Burlington ON) 19 ACS Paragon Plus Environment
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434
for sediment core dating. We thank Neal Tanna (Canadian Oil Sands Innovation Alliance
435
(COSIA), Calgary AB) and Kelly Munkittrick (formerly with COSIA, now Wilfrid Laurier
436
University, Waterloo ON) and staff of SUNCOR and CNRL, for provision of AOSR mining
437
ores, pet coke and haul road dust, Jonathan Martin (Stockholm University) and Yifeng Zhang
438
(University of Alberta) for provision of the Anzac and fluidized petcoke source samples, and
439
Narumol Jariyasopit (ECCC, Toronto ON) for concentration calculations on the passive air
440
samples.
441 442
References
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29. Bleeker, E.; Pieters, B.; Wiegman, S.; Kraak, M., Comparative (photoenhanced) toxicity of homocyclic and heterocyclic PACs. Polycyclic Aromat. Compd. 2002, 22, (3-4), 601-610. 30. Bleeker, E. A.; Wiegman, S.; de Voogt, P.; Kraak, M.; Leslie, H. A.; de Haas, E.; Admiraal, W., Toxicity of azaarenes. Rev. Environ. Contam. Toxicol. 2001, 173, 39-83. 31. Chlebowski, A. C.; Garcia, G. R.; La Du, J. K.; Bisson, W. H.; Truong, L.; Massey Simonich, S. L.; Tanguay, R. L., Mechanistic investigations into the developmental toxicity of nitrated and heterocyclic PAHs. Toxicol. Sci. 2017, 157, (1), 246-259. 32. Pašková, V.; Hilscherová, K.; Feldmannová, M.; Bláha, L., Toxic effects and oxidative stress in higher plants exposed to polycyclic aromatic hydrocarbons and their N-heterocyclic derivatives. Environ. Toxicol. Chem. 2006, 25, (12), 3238-3245. 33. Wassenberg, D. M.; Nerlinger, A. L.; Battle, L. P.; Di Giulio, R. T., Effects of the polycyclic aromatic hydrocarbon heterocycles, carbazole and dibenzothiophene, on in vivo and in vitro cypia activity and polycyclic aromatic hydrocarbon-derived embryonic deformities. Environ. Toxicol. Chem. 2005, 24, (10), 2526-2532. 34. Kirk, J. L.; Muir, D. C.; Gleason, A.; Wang, X.; Lawson, G.; Frank, R. A.; Lehnherr, I.; Wrona, F., Atmospheric deposition of mercury and methylmercury to landscapes and waterbodies of the Athabasca oil sands region. Environ. Sci. Technol. 2014, 48, (13), 7374-7383. 35. Canada-Alberta Oil Sands Environmental Monitoring Program. https://www.canada.ca/en/environment-climate-change/services/oil-sands-monitoring.html 36. Cong, X.; Yang, G.; Qu, J.; Dai, M., Evaluating the dynamical characteristics of particle matter emissions in an open ore yard with industrial operation activities. Environ. Sci. Pollut. Res. Int. 2016, 23, (21), 21336-21349. 37. Mandal, K.; Kumar, A.; Tripathi, N.; Singh, R.; Chaulya, S.; Mishra, P.; Bandyopadhyay, L., Characterization of different road dusts in opencast coal mining areas of India. Environ. Monit. Assess. 2012, 184, (6), 3427-3441. 38. Anthony, E., Fluidized bed combustion of alternative solid fuels; status, successes and problems of the technology. Prog. Energy Combust. Sci. 1995, 21, (3), 239-268. 39. Shang, D.; Kim, M.; Haberl, M., Rapid and sensitive method for the determination of polycyclic aromatic hydrocarbons in soils using pseudo multiple reaction monitoring gas chromatography/tandem mass spectrometry. J. Chromatogr. A 2014, 1334, 118-125. 40. Manzano, C. A.; Muir, D.; Marvin, C., Separation of thia-arenes and aza-arenes from polycyclic aromatics in snowpack samples from the Athabasca oil sands region by GC× GC/ToF-MS. Int. J. Environ. Anal. Chem. 2016, 96, (10), 905-920. 41. Samanipour, S.; Dimitriou-Christidis, P.; Gros, J.; Grange, A.; Arey, J. S., Analyte quantification with comprehensive two-dimensional gas chromatography: Assessment of methods for baseline correction, peak delineation, and matrix effect elimination for real samples. J. Chromatogr. A 2015, 1375, 123-139. 42. Manzano, C.; Hoh, E.; Simonich, S. L. M., Improved separation of complex polycyclic aromatic hydrocarbon mixtures using novel column combinations in GC× GC/ToF-MS. Environ. Sci. Technol. 2012, 46, (14), 7677-7684. 43. Lintelmann, J.; França, M. H.; Hübner, E.; Matuschek, G., A liquid chromatography–atmospheric pressure photoionization tandem mass spectrometric method for the determination of azaarenes in atmospheric particulate matter. J. Chromatogr. A 2010, 1217, (10), 1636-1646. 44. Hughey, C. A.; Hendrickson, C. L.; Rodgers, R. P.; Marshall, A. G.; Qian, K., Kendrick mass defect spectrum: a compact visual analysis for ultrahigh-resolution broadband mass spectra. Anal. Chem. 2001, 73, (19), 4676-4681. 45. Thienpont, J. R.; Desjardins, C. M.; Kimpe, L. E.; Korosi, J. B.; Kokelj, S. V.; Palmer, M. J.; Muir, D. C.; Kirk, J. L.; Smol, J. P.; Blais, J. M., Comparative histories of polycyclic aromatic compound 22 ACS Paragon Plus Environment
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Tables and Figures TOC/Abstract Art
Athabasca Oil Sands
Snow
1
0.1
Oil sand
Petcoke
0.01
0.001
0.0001
NH
N
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Environmental Science & Technology
1
A.
Kendrick Mass Defect (-CH2)
0.95
E
0.9
C A .
D
0.85
B .
0.8 0.75 0.7 0.65 0.6
160
180
200
220
240
m/z
260
280
1
B. Kendrick Mass Defect (-CH2)
0.95
E
0.9
C A
D
B
0.85
0.8
0.75
0.7 160
180
200
220
240
260
280
m/z
Figure 1. Kendrick mass defect plot (KMD) of snowpack sample nearest main upgrading and mining activities in the Athabasca Oil Sands with data from in LC-HRMS analysis in (A) negative and (B) positive mode, showing the NPAC isomer classes (red). The 5 most abundant classes by composition detected by GC×GC/ToF-MS are labelled as follows: A (C17H13N, 19%), B (C18H15N, 15%), C (C14H13N, 13%), D (C16H11N, 12%), E (C13H11N, 11%).
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60
Total NPACs, ng/g
50 40 30 20 10 0
1905
1920
1935
1950
1965
1980
1995
2010
2025
Year
Figure 2. ΣNPAC concentrations (ng/g dry wt) in a dated sediment core from Lake NE20 vs year. Horizontal error bars represent 1 SD for the estimated median age of the sediment sample.
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0.30
A.
Distance from AR6, R2 = 0.70 Distance to nearest source, R2 = 0.68
0.25
6
0.20
4
0.15
2
0.10
0
0.05
40
60
80
100
Distance, km
60.1 (AMS 14)
20
24.5 (AMS 6)
0.00 0
8 (AMS 13)
-2
6.6 (AMS 9)
Ln (Total NPACs, pg/uL)
8
B.
3.7 (AMS 5)
10
Distance from nearest source, km (site)
Figure 3. ΣNPAC concentrations in (A) snowpack samples as a function of distance from AR6 (red dashed line), and from nearest source (i.e. mine, stack) (black dashed line) based on exponential decay function, f = ae (-bx), and (B) passive air samples vs distance to nearest source.
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1
0.1
A. Petcoke 1
I.
G. Roaddust
D. Oil Sands Ore 1
II.
III.
IV. I.
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II.
III.
IV. I.
J. Sediment (0-8 cm), n = 3
II.
III.
IV. I.
II.
III.
IV.
0.01
0.001
log (Composition fraction)
0.0001 1
B. Petcoke 2
E. Oil Sands Ore 2
C. Petcoke 3
F. Oil Sands Ore 3
H. Snowpack (0-10 km), n = 8
H. K. Passive air (AMS 5, 6.6 km)
I. Snowpack (50 - 80 km), n = 7
L. Passive air (AMS 13, 16.1 km)
0.1
0.01
0.001
0.0001 1
C.
X Data
0.1
0.01
0.001
0.0001
Figure 4. Log composition fraction (individual concentration divided by total NPACs) of carbazoles in (A-G) delayed petcoke, oil sands mineral ores and road dust source materials, average composition fraction of snowpack sites within (H) 0-10 km and (I) 50-80 km of AR6, (J) average composition fraction of top 3 sections of sediment core and (K, L) passive air samples. The x-axis in each plot represents the individual isomers sub-grouped as I- carbazole and methylcarbazoles, II – dimethylcarbazoles and ethylcarbazoles, III – trimethylcarbazoles, and IV – benzocarbazoles and phenylcarbazoles (increasing molecular weight from left to right). Source materials were provided by the Canadian Oil Sands Innovation Alliance and obtained from a site near an upgrading facility near Anzac, Alberta.
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A. 5
10
Snow (AR6)
Sediment (top sections)
B.
5 Passive air (AMS-5)
PC 3 (7.76%)
PC 2 (22.99%)
0
-5
Snow (AR6)
Sediment (top sections)
0
-5 -10 Passive air (AMS-5)
-10
-15
-15
-20 -10
-5
0
5 PC 1 (25.51%)
10
15
-10
-5
0 5 PC 1 (25.51%)
10
Figure 5. (A) PC1 vs PC2 and (B) PC1 vs PC3 score plots for 133 compounds of the most abundant NPAC isomer classes in each source material. (Loadings plot is shown in Figure S7).
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