Statistical Analysis of Reduced Sulphur Compounds...Bureau Veritas Laboratories analyzed all samples for 19 reduced sulphur compounds (Table 1), and quantified amounts of unidentified

Statistical Analysis of Reduced Sulphur Compounds

Context

The Froth Treatment Tailings (FTT) working group of COSIA has executed a number of field sampling programs since 2017 to further understanding of the bio-geochemical behaviour of FTT in tailings deposits. A subset of the analyses done focused on characterizing the microbiology present in the sediment layers, as well as the degradation products resulting from the bioconversion of residual light hydrocarbons in the tailings. A significant finding was that for older ponds, the gaseous compounds (e.g. N2, CH4, CO2, H2S) could exceed the tailings pore water solubility limit leading to a potential free gas phase in the tailings. The gas phase (in the form of small gas bubbles) can remain in the sediment layer due to the fact that their net buoyancy force is not strong enough to overcome the yield stress in the sediment layer. The composition of the accumulated gas can be used as an independent metric for the biodegradation pathways that are occurring in the sediment layer.

While the sampling programs were not initially intended to assess reduced sulfur compounds, the information has proven useful to provide screening level information of the distribution (within ponds, as a function of depth) and concentration of a number of compounds. The information is made available as a resource for potential follow-up research. The reader is cautioned that the data refer to in-situ compositions only: the data set does not address gas generation/release rates from the sediment layer, nor any oxidative processes that may occur in the overlaying water cap.

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1.0 INTRODUCTION 1.1 Background In 2018, Canada’s Oil Sands Innovation Alliance (COSIA) contracted Golder Associates Ltd. (Golder) and InnoTech Alberta (InnoTech) to undertake a regional assessment of environmental aspects of Froth Treatment Tailings (FTT) deposits. As part of this assessment, reduced sulphur species were analyzed on the gas phase released from FTT samples collected from three operations.

In oil sands tailings, hydrogen sulphide (H2S) and other reduced sulphur compounds are produced through biological decomposition of organic sulphur compounds and the reduction of inorganic sulphur compounds by sulphur reducing microbes. Hydrogen sulphide is considered a substance of concern because it presents an acute health and safety risk, is corrosive and can damage industrial infrastructure (e.g., steel), and can cause odour issues at low concentrations (odour threshold of 0.41 ppb; Alberta Energy Regulator [AER] 2016). In addition to H2S, other reduced sulphur compounds such as thiophene and mercaptans (e.g., butanethiol) have strong odours at low concentrations (odour thresholds of 0.56 ppb and 0.03 ppb, respectively; AER 2016) and can be transported off site in the atmosphere.

Residents of Fort McKay have expressed human health concerns related to air quality and odours around oil sands operations, and a report by the AER and Alberta Health (AER 2016) noted that some of the odours in the area could originate from tailings ponds. This technical memorandum was not completed as part of that AER initiative, but it provides the COSIA FTT Working Group members with additional information relevant to this topic.

Note that not all the Reduced Sulphur Compounds (RSC) parameters of interest identified by the Fort McKay residents were included in the COSIA FTT analytical program. The full list of RSC parameters of interest outlined in Table 32 of AER (2016), as compared to those included in the COSIA FTT analytical program, are shown in Table 1. Also, the detection limits associated with the RSC compounds analyzed as part of the COSIA program are, in many cases, much higher than the odour thresholds outlined in AER 2016. The scope of this memo is to summarize the RSC data collected as part of the COSIA FTT program and to coarsely quantify unidentified RSC compounds, it does not include an assessment of risk or likelihood of odour detection.

TECHNICAL MEMORANDUM DATE 22 March 2021 Project No. 1779008

TO Lucas Barr, Elco Hollander, and Ryan Bouma COSIA Froth Treatment Working Group

FROM Skya Fawcett and Matt Neuner EMAIL [email protected]

STATISTICAL ANALYSIS OF REDUCED SULPHUR COMPOUNDS

Lucas Barr, Elco Hollander, and Ryan Bouma Project No. 1779008

COSIA Froth Treatment Working Group 22 March 2021

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1.2 Objectives and Approach The overall objective of the work herein is to provide statistical information about reduced sulphur compounds that may be present in tailings at the sites and may be considered problematic with reference to emissions, hazard levels for workers, odour, and/or human health concerns for the region.

To address this objective, the following steps were completed:

Accounting of all reduced sulphur species present in the current COSIA FTT dataset and where they occur in detectable quantities.

Statistical analysis of reduced sulphur species, including mean, median, mode, and 98th percentile for each reduced sulphur compound.

Comparison of statistical analyses between ponds.

Laboratory review of the raw chromatograms to identify the likely number of unidentified compounds in several groups of compounds.

2.0 METHODS Gas samples were extracted from 364 sealed sample bags containing FTT tailings samples collected at depth from several tailings storage facilities.

Reduced sulphur compounds in the extracted gas samples were analyzed via gas chromatography and sulphur chemiluminescence (ASTM D5504) by Bureau Veritas Laboratories in Edmonton, Alberta in 2018.

Bureau Veritas Laboratories analyzed all samples for 19 reduced sulphur compounds (Table 1), and quantified amounts of unidentified compounds into five groups. Unidentified compounds are reduced sulphur compounds other than the 19 listed in Table 1, which were partially identified and classified by the number of carbon (C) atoms in their chemical structures.

As a point of clarification, the term unidentified refers to a compound that was detected as being present, but the exact compound detected could not be identified. The term non-detect refers to a compound that had concentration lower than the detection limit.

Further analysis of unidentified compounds was conducted via additional review of the sulphur chemiluminescence chromatograms for 126 samples to provide a more thorough classification of the unidentified compounds. These 126 samples were selected from the 364 total samples to provide a spatially representative subset of the data with a focus on samples with higher concentrations of unidentified compounds. For this analysis, Bureau Veritas Laboratories counted and reported the number of peaks on each chromatogram corresponding to the likely number of different compounds detected in each compound group but for which the specific compound was not be identified. The result of this additional review was to report the likely number of unidentified compounds per group, in addition to the concentration values for the total unidentified compounds in each group. This additional analysis indicates whether concentrations of unidentified parameters may be attributable to one or more different compounds for each of the unidentified groups. Multiple unidentified compounds may be contained within each boiling point grouping (e.g., more than one C4 compound in the 71 to 97 degrees Celsius (°C) boiling point category).



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Table 1: Proposed Compounds for Analysis Requested Compound -

COSIA Included in COSIA FTT analytical

program? Chemical Formula

Odor threshold (AER 2016)

Detection limit

Unit ppbv ppm mass

Hydrogen Sulphide Yes H2S 0.41 0.5

Methyl mercaptan Yes CH3SH N/A 0.5

Carbonyl sulphide Yes COS 55 0.5

Dimethyl sulphide Yes C2H6S 1 0.5

Ethyl mercaptan Yes C2H6S 0.0087 0.5

Thiourea Not available CH4N2S N/A N/A

Carbon disulphide Yes CS2 8 0.5

Propyl mercaptan Yes C3H8S 0.013 0.5

Ethyl methyl sulphide Yes C3H8S 0.5

Isopropyl mercaptan Yes C3H8S 0.006 0.5

Thiophene Yes (combined result with sec-butyl mercaptan) C4H4S 0.56 0.5

Thiophene, tetrahydro- Not available C4H8S N/A N/A

Isobutyl mercaptan Yes C4H10S 0.0068 0.5

Butyl mercaptan Yes C4H10S 0.029 0.5

Diethyl sulphide Yes C4H10S 0.033 0.5

sec-Butyl mercaptan Yes (combined result with thiophene) C4H10S 0.03 0.5

tert-Butyl mercaptan Yes C4H10S 0.029 0.5

Dimethyl disulphide Yes C2H6S2 0.2 0.5

2-methyl Thiophene Not available C5H6S 0.56 N/A

3-methyl Thiophene Not available C5H6S 0.56 N/A

Thiophene, tetrahydro-2-methyl- Not available C5H10S N/A N/A

Pentyl mercaptan Yes C5H12S 0.0078 0.5

tert-Pentyl mercaptan Not available C5H12S 0.03 N/A

Methyl ethyl disulphide Not available C3H8S2 N/A N/A

Benzenethiol Not available C6H6S N/A N/A

Benzenethiol-S-D Not available C6H5DS N/A N/A

Thiophene, 3,4-dimethyl- Not available C6H8S 0.56 N/A



2,5-dimethyl Thiophene Not available C6H8S 0.56 N/A

Thiophene, 2-ethyl- Not available C6H8S 0.56 N/A



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Detection limit

Unknown Sulphur 3** Not available N/A N/A

Thiophene, 3-ethyl- Not available C6H8S 0.56 N/A

Unknown Sulphur 2** Not available N/A N/A

Diallyl sulphide Not available C6H10S 0.02 N/A

Thiophene, tetrahydro-2,5-d Not available C6H12S N/A N/A

Hexyl mercaptan Yes C6H14S N/A 0.5

Disulfide, methyl propyl Not available C4H10S2 N/A N/A

Diethyl disulphide Not available C4H10S2 N/A N/A

Thiophene, 2-ethyl-5-methyl- Not available C7H10S N/A N/A

Thiophene, 2-(1-methylethyl)- Not available C7H10S N/A N/A

2-ethyl-4-methylthiophene Not available C7H10S N/A N/A

Thiophene, 2,3,4-trimethyl- Not available C7H10S N/A N/A

Thiophene, 2,3,5-trimethyl- Not available C7H10S N/A N/A

Dimethyl trisulphide Not available C2H6S3 N/A N/A

Heptyl mercaptan Yes C7H16S N/A 0.5

Benzothiophene Not available C8H6S N/A N/A

Ethyl n-propyl disulfide Not available C5H12S2 N/A N/A

Methyl tert-butyl disulphide Not available C5H12S2 N/A N/A

Disulfide, ethyl 1-methyl Not available C6H14S2 N/A N/A

Thiophene, 2-methyl-5-propyl- Not available C8H12S N/A N/A

Thiophene, 2,5-diethyl- Not available C8H12S N/A N/A

Octyl mercaptan Not available C8H18S N/A N/A

Dibutyl sulphide Not available C8H18S N/A N/A

5-methyl benzothiophene Not available C9H8S N/A N/A

3-methyl benzothiophene Not available C9H8S N/A N/A

Dipropyl disulfide Not available C6H14S2 N/A N/A

Thiophene, 2-propyl- Not available C11H12S N/A N/A

Methyl Propyl Trisulphide Not available C4H10S3 N/A N/A

Dimethyl tetrasulphide Not available C2H6S4 N/A N/A

n-Propyl sec-butyl disulphide Not available C7H16S2 N/A N/A

n-Propyl n-butyl disulphide Not available C7H16S2 N/A N/A



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Detection limit

Dibutyl disulphide Not available C8H18S2 N/A N/A

Di-n-octyl disulfide Not available C16H34S2 N/A N/A Note: odour thresholds are from AER (2016) table 32, N/A = Not Applicable.

3.0 RESULTS 3.1 Statistical Analysis of Reduced Sulphur Compounds Statistical analysis was performed to assess quantities of reduced sulphur compounds present. Ten of the parameters analyzed (Table 1) were not detected in any samples and are listed in Table 2. For statistical analysis, samples were grouped by pond, Appendix A contains all statistical calculation results. For each sample grouping, the following statistics were calculated: mode, median, mean, 98th percentile, and count. All modes were equal to values below detection, except for carbonyl sulphide in Pond A and E (Appendix A). Example histograms in Figure 1 show that even for compounds with higher detected concentrations in Tables 3 and 4, the majority of values were below detection (e.g., hydrogen sulphide, carbonyl sulphide, thiophene/sec-butanethiol, thiosulphates, and unidentified groups with four, five, and six carbon atoms), the RSC dataset is not normally distributed.

Table 3 contains a comparison of statistical results for samples with identified reduced sulfur compounds, median and 98th percentile values, with percentages of samples that returned values greater than the detection limit. Table 4 contains a similar statistical comparison for compounds that were detected in the dataset but not identified by the laboratory.

Key results in reduced sulphur statistics for identified compounds include:

Carbonyl sulphide was the most commonly detected reduced sulphur compound, followed by hydrogen sulphide and thiosulphates.

Percentages of samples with reduced sulphur compounds above detection vary between ponds, as do the types of compounds detected.

Most median values were equal to the detection limit, with some exceptions (Table 3).

Carbonyl sulphide 98th percentile concentrations were greater than detection limits in all sample groups and concentrations are notably less variable for this parameter across the entire dataset (98th percentile range 0.58 to 9.5 ppm mass) (Table 3).

Thiosulphates and hydrogen sulphide are the only two parameters that occur in concentrations greater than 100 ppm mass in some samples in the dataset. Hydrogen sulphide concentrations are similar to thiosulphate concentrations in samples from ponds E and F (Table 3).



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Table 2: Reduced Sulphur Compounds Analyzed, Not Detected Parameter Formula

ethanethiol (ethyl mercaptan) C₂H₆S

iso-butanethiol (isobutyl mercaptan) C4H10S

iso-propanethiol (isopropyl mercaptan) C3H8S

methyl disulphide C2H6S2

methyl ethyl sulphide C3H8S

methyl sulphide C2H6S

n-butanethiol (butyl mercaptan) C4H10S

n-heptanethiol (heptyl mercaptan) C7H16S

n-hexanethiol (hexyl mercaptan) C6H14S

n-pentanethiol (pentyl mercaptan) C5H12S

n-propanethiol (propyl mercaptan) C3H8S

t-butanethiol (tert-butyl mercaptan) C4H10S



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Notes: The X-axis represents increasing reduced sulphur concentrations to the right, while the Y-axis shows increasing numbers of samples. For reduced sulphur compounds, most values are generally below detection or near the detection limit.

Figure 1: Two conceptual histograms of Reduced Sulphur Compound Data Distributions, the RSC data tend to be distributed according to one or the other.



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Table 3: Median, 98th Percentile, and Percentage of Values Greater than Detection for Identified Reduced Sulphur Compounds

Pond

Parameter Hydrogen Sulfide Carbon Disulfide Carbonyl Sulphide Diethyl Sulphide Iso-Butanethiol (Isobutyl Mercaptan)

Iso-Propanethiol (Isopropyl Mercaptan)

Methyl Disulfide Thiomethanol Thiophene/sec-

Butanethiol (Sec-Butyl Mercaptan)

Thiosulphates

Chemical Formula H2S CS2 COS C4H10S C4H10S C3H8S C2H6S2 CH4S C4H10S S2O32-

units ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass

Detection limit 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 5

Pond A

98th Percentile 6.8 <0.5 2.9 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 8.8

Median <0.5 <0.5 0.6 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <5

Percent >DL 21% 0% 58% 0% 0% 0% 0% 0% 0% 11%

Pond B

98th Percentile <0.5 <0.5 0.9 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 5.8

Median <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <5

Percent >DL 5% 0% 23% 1% 0% 0% 0% 0% 0% 2%

Pond C

98th Percentile 0.78 <0.5 3.0 <0.5 <0.5 <0.5 0.85 <0.5 4.2 14

Median <0.5 <0.5 0.7 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <5

Percent >DL 16% 0% 78% 0% 0% 0% 6% 3% 53% 44%

Pond D

98th Percentile 37 <0.5 3.2 <0.5 <0.5 <0.5 <0.5 <0.5 1.0 66

Median <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <5

Percent >DL 25% 0% 32% 2% 0% 0% 0% 0% 5% 37%

Pond E

98th Percentile 757 2.8 3.8 <0.5 0.85 <0.5 <0.5 <0.5 <0.5 761

Median 22 <0.5 0.85 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 25

Percent >DL 81% 6% 94% 0% 6% 0% 0% 0% 0% 75%

Pond F

98th Percentile 341 1.8 9.5 7.2 <0.5 <0.5 <0.5 <0.5 <0.5 366

Median <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <5

Percent >DL 25% 1% 12% 1% 1% 0% 0% 0% 0% 21%

Note: DL = detection limit; >= greater than. Cells containing values above detection are shaded from light (low values) to dark (high values) as a qualitative comparison to the entire dataset. Statistics were calculated by replacing values below detection with the detection limit.



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Table 4: Median, 98th Percentile, and Percentage of Values Above Detection for Unidentified Reduced Sulphur Compounds

Pond

Parameter Boiling point

36-69 degrees C

Boiling point 71-97

degrees C

Boiling point 100-126

degrees C


degrees C


degrees C

Chemical Formula Unidentified C3 Unidentified C4 Unidentified C5 Unidentified C6 Unidentified C7

units ppm mass ppm mass ppm mass ppm mass ppm mass

Detection limit 0.5 0.5 0.5 0.5 0.5

Pond A

98th Percentile <0.5 <0.5 <0.5 <0.5 <0.5

Median <0.5 <0.5 <0.5 <0.5 <0.5

Percent >DL 0% 0% 0% 0% 0%

Pond B

98th Percentile <0.5 3.7 <0.5 <0.5 0.92

Median <0.5 <0.5 <0.5 <0.5 <0.5

Percent >DL 0% 7% 0% 0% 2%

Pond C

98th Percentile <0.5 <0.5 4.6 4.3 1.3

Median <0.5 <0.5 1.2 1.2 <0.5

Percent >DL 0% 0% 74% 71% 25%

Pond D

98th Percentile <0.5 15 21 18 <0.5

Median <0.5 <0.5 <0.5 <0.5 <0.5

Percent >DL 1% 15% 41% 19% 0%

Pond E

98th Percentile <0.5 2.3 2.4 1.5 <0.5

Median <0.5 <0.5 <0.5 <0.5 <0.5

Percent >DL 0% 31% 50% 13% 0%

Pond F

98th Percentile <0.5 7.9 12 25 1.5

Median <0.5 <0.5 0.7 <0.5 <0.5

Percent >DL 0% 9% 25% 22% 3%

Note: DL = detection limit; >= greater than. Cells containing values above detection are shaded from light (low values) to dark (high values) as a qualitative comparison to the entire dataset (including identified compounds in Table 3). Statistics were calculated by replacing values below detection with the detection limit.



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3.2 Unidentified Reduced Sulphur Compounds Appendix B contains results from analysis of unidentified compounds in 126 samples of the COSIA FTT dataset. Unidentified compounds were initially grouped into five categories corresponding to boiling points and the number of carbon atoms per molecule (Table 4). Results reported in Appendix B present the number of different compounds (zero to four) identified as distinct peaks in the chromatograms within each group of unidentified compounds, alongside concentration values for each group (i.e., concentration values for the sum of all compounds within the group of unidentified compounds). Results are summarized in Table 5.

Key results include:

All Pond A samples submitted had concentrations below detection.

Pond B samples contained one unidentified peak in the C4 and C7 groups.

The unidentified C6 group was the only group of unidentified compounds to contain more than two unidentified peaks (compounds).



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Table 5: Unidentified Peaks Summary Table

Pond Number of Samples Statistic Unidentified

C3 Unidentified

C4 Unidentified

C5 Unidentified

C6 Unidentified

C7

Boiling Point 36 – 69 71 – 97 100 – 126 127 – 150 152 – 176

Pond A 4 Number of Samples >DL 0 0 0 0 0

Number of Peaks within the group N/A N/A N/A N/A N/A

Pond B 10 Number of Samples >DL 0 4 0 0 1

Number of Peaks within the group N/A 1 N/A N/A 1

Pond C 18 Number of Samples >DL 0 2 14 13 3

Number of Peaks within the group N/A 1 1 to 2 1 to 4 1 to 2

Pond D 50 Number of Samples >DL 1 11 30 17 0

Number of Peaks within the group 1 1 to 2 1 to 2 1 to 4 N/A

Pond E 11 Number of Samples >DL 0 4 5 1 0

Number of Peaks within the group N/A 1 1 to 2 4 N/A

Pond F 33 Number of Samples >DL 0 8 26 24 2

Number of Peaks within the group N/A 1 1 1, 3, or 4 1 to 2

Note: N/A = Not Applicable



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4.0 DISCUSSION AND SUMMARY 4.1 Unidentified Reduced Sulphur Compounds As reported in Section 3.2, unidentified reduced sulphur compound groupings may contain multiple different compounds. Table 6 lists reduced sulphur compounds containing between three and seven carbon atoms in their molecular structure that Bureau Veritas were not able to analyze (see Table 1). Unidentified reduced sulphur compound group concentrations thus may be made up of compounds included in Table 6 but may not be limited to these.

Table 6: Reduced Sulphur Compounds With 3 - 7 Carbon Atoms, Not Analyzed by Laboratory Carbon Atoms

Boiling Point Grouping Compound Chemical

Formula Comment

3 36-69 °C Methyl ethyl disulphide C3H8S2 -

4 71-97 °C

Disulphide, methyl propyl C4H10S2 - Diethyl disulphide C4H10S2 - Methyl Propyl Trisulphide C4H10S3 - Thiophene, tetrahydro- C4H8S -

5 100-126 °C

Thiophene, tetrahydro-2-methyl- C5H10S - tert-Pentyl mercaptan C5H12S - Ethyl n-propyl disulphide C5H12S2 - Methyl tert-butyl disulphide C5H12S2 -

2-methyl Thiophene C5H6S Odourant Focal Parameter (AER 2016)

3-methyl Thiophene C5H6S Odourant Focal Parameter (AER 2016)

6 127-150 °C

Diallyl sulphide C6H10S - Thiophene, tetrahydro-2,5-d C6H12S - Disulphide, ethyl 1-methyl C6H14S2 - Dipropyl disulphide C6H14S2 - Benzenethiol C6H6S - Thiophene, 3,4-dimethyl- C6H8S - Thiophene, 2,3-dimethyl- C6H8S - Thiophene, 2,4-dimethyl- C6H8S - 2,5-dimethyl Thiophene C6H8S - Thiophene, 2-ethyl- C6H8S - Thiophene, 3-ethyl- C6H8S -

7 152-176 °C

Thiophene, 2-(1-methylethyl)- C7H10S - Thiophene, 2-ethyl-5-methyl- C7H10S - 2-ethyl-4-methylthiophene C7H10S - Thiophene, 2,3,4-trimethyl- C7H10S - Thiophene, 2,3,5-trimethyl- C7H10S - n-Propyl sec-butyl disulphide C7H16S2 - n-Propyl n-butyl disulphide C7H16S2 -

Notes: °C = degrees Celsius; C = carbon, H = hydrogen, S = sulphur.



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4.2 Summary Differences in reduced sulphur compound types and abundances in the overall dataset generally vary between ponds. Key reduced sulphur compounds present include:

hydrogen sulphide

thiosulphates

carbonyl sulphide

unidentified C6 compounds (up to four compounds)

unidentified C5 compounds (up to two compounds)

unidentified C4 compounds (up to two compounds)

lesser amounts of carbon disulphide, diethyl sulphide, iso-butanethiol (isobutyl mercaptan), methyl disulphide, thiophene/sec-butanethiol (sec-butyl mercaptan), unknown C7 compounds, and unidentified C3 compounds.

The typical data distribution for reduced sulphur parameters is that most compounds are below detection most of the time.



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SIGNATURE PAGE

Golder Associates Ltd.

Mackenzie Bromstad, M.Sc. Geochemistry Consultant

Matt Neuner, M.Sc. Skya Fawcett, Ph.D., P.Geo. Senior Geochemistry Consultant Associate, Senior Geochemist

MB/MN/SF/rd/tt/dh

Appendix A: Detailed Statistical Results Appendix B: Investigation of Unidentified Compounds



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References AER (Alberta Energy Regulator). 2016. Recurrent Human Health Complaints Technical Information Synthesis –

Fort McKay Area. Report prepared by the AER and Alberta Health for residents of Fort McKay and oil sands stakeholders, published by the AER, September 2016. 257p. Available at: https://www.aer.ca/protecting-what-matters/reporting-on-our-progress/improving-air-quality-and-odours-in-fort-mckay.html. Accessed: April 2020.

https://www.aer.ca/protecting-what-matters/reporting-on-our-progress/improving-air-quality-and-odours-in-fort-mckay.html

https://www.aer.ca/protecting-what-matters/reporting-on-our-progress/improving-air-quality-and-odours-in-fort-mckay.html



APPENDIX A

Detailed Statistical Results

March 2021 1779008

Parameter Hydrogen Sulfide Carbon Disulfide Carbonyl Sulphide Diethyl SulphideEthanethiol (Ethyl Mercaptan)

Iso-Butanethiol (Isobutyl Mercaptan)

Iso-Propanethiol (Isopropyl Mercaptan) Methyl Disulfide

Methyl Ethyl Sulphide Methyl Sulfide

n-Butanethiol (Butyl Mercaptan)

n-Heptanethiol (Heptyl Mercaptan)

n-Hexanethiol (Hexyl Mercaptan)

Chemical Formula H2S CS2 COS C4H10S C₂H₆S C4H10S C3H8S C2H6S2 C3H8S C2H6S C4H10S C7H16S C6H14SUnit ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm massDetection limit 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5Median <0.5 <0.5 0.6 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mean 1.3 <0.5 0.85 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mode <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.598th Percentile 6.8 <0.5 2.9 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Count 19 19 19 19 19 19 19 19 19 19 19 19 19Median <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mean 0.5 <0.5 0.54 0.51 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mode <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.598th Percentile <0.5 <0.5 0.9 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Count 87 87 87 87 87 87 87 87 87 87 87 87 87Median <0.5 <0.5 0.7 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mean 0.52 <0.5 0.99 <0.5 <0.5 <0.5 <0.5 0.53 <0.5 <0.5 <0.5 <0.5 <0.5Mode <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.598th Percentile 0.78 <0.5 3.0 <0.5 <0.5 <0.5 <0.5 0.85 <0.5 <0.5 <0.5 <0.5 <0.5Count 32 32 32 32 32 32 32 32 32 32 32 32 32Median <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mean 3.7 <0.5 0.8 0.62 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mode <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.598th Percentile 37 <0.5 3.2 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Count 110 110 110 110 110 110 110 110 110 110 110 110 110Median 22 <0.5 0.85 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mean 171 0.71 1.6 <0.5 <0.5 0.53 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mode <0.5 <0.5 0.7 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.598th Percentile 757 2.8 3.8 <0.5 <0.5 0.85 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Count 16 16 16 16 16 16 16 16 16 16 16 16 16Median <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mean 71 0.63 1.2 0.92 <0.5 0.51 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Mode <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.598th Percentile 341 1.8 9.5 7.2 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Count 104 104 104 104 104 104 104 104 104 104 104 104 104

Pond F

Pond B

Pond A

Facility

Pond C

Pond D

Pond E

Page 1 of 2

March 2021 1779008

ParameterChemical FormulaUnitDetection limitMedianMeanMode98th PercentileCountMedianMeanMode98th PercentileCountMedianMeanMode98th PercentileCountMedianMeanMode98th PercentileCountMedianMeanMode98th PercentileCountMedianMeanMode98th PercentileCount

Pond F

Pond B

Pond A

Facility

Pond C

Pond D

Pond E

n-Pentanethiol (Pentyl Mercaptan)

n-Propanethiol (Propyl Mercaptan)

t-Butanethiol (Tert-Butyl Mercaptan) Thiomethanol

Thiophene/sec-Butanethiol (Sec-Butyl Mercaptan) Thiosulphates

Boiling point 36-69 degrees (Unknown C3)





C5H12S C3H8S C4H10S CH4S C4H10S S2O32- C3 (Unknown) C4 (Unknown) C5 (Unknown) C6 (Unknown) C7 (Unknown)ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass ppm mass

0.5 0.5 0.5 0.5 0.5 5 0.5 0.5 0.5 0.5 0.5<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 5.4 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 8.8 <0.5 <0.5 <0.5 <0.5 <0.519 19 19 19 19 19 19 19 19 19 19

<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 5.1 <0.5 0.68 <0.5 <0.5 0.55<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 5.8 <0.5 3.7 <0.5 <0.5 0.9287 87 87 87 87 87 87 87 87 87 88

<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 1.2 1.4 <0.5<0.5 <0.5 <0.5 <0.5 1.0 6.4 0.53 <0.5 1.5 1.5 0.61<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 4.2 14 0.8 <0.5 4.6 4.2 1.332 32 32 32 32 32 32 32 32 32 32

<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 0.53 12 0.51 1.6 3.1 2.2 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 1.0 66 <0.5 15 21 18 <0.5110 110 110 110 110 110 110 110 110 110 110<0.5 <0.5 <0.5 <0.5 <0.5 25 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 175 <0.5 0.89 0.96 0.6 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 761 <0.5 2.3 2.4 1.5 <0.516 16 16 16 16 16 16 16 16 16 16

<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 0.7 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 84 <0.5 1.6 3.6 5.4 0.66<0.5 <0.5 <0.5 <0.5 <0.5 <5 <0.5 <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 <0.5 366 <0.5 7.9 12 25 1.5104 104 104 104 104 104 104 104 104 104 104

Page 2 of 2



APPENDIX B

Investigation of Unidentified Compounds

January 2021 1779008

Boiling point 36-69 degrees

CUnknown C3

Boiling point 71-97 degrees

CUnknown C4


degrees CUnknown C5


degrees CUnknown C6


degrees CUnknown C7

ppm_mass Number of Peaks ppm_mass Number of

Peaks ppm_mass Number of Peaks ppm_mass Number of

Peaks ppm_mass Number of Peaks

6 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 02.9 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 04.8 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 04.3 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0

11.8 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 08 < 0.5 0 1.9 1 < 0.5 0 < 0.5 0 < 0.5 0

3.6 < 0.5 0 1.7 1 < 0.5 0 < 0.5 0 < 0.5 01.6 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 01.8 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 00.6 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 03.6 < 0.5 0 3.1 1 < 0.5 0 < 0.5 0 < 0.5 03.9 < 0.5 0 5.4 1 < 0.5 0 < 0.5 0 2.1 1

11.9 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 018.9 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 010.6 < 0.5 0 < 0.5 0 1 1 < 0.5 1 < 0.5 011.6 < 0.5 0 < 0.5 1 0.9 1 0.8 2 < 0.5 012.6 < 0.5 0 < 0.5 0 1.4 2 1.6 2 < 0.5 113.6 < 0.5 0 < 0.5 0 0.9 1 1.8 2 (1 UR) < 0.5 014.6 < 0.5 0 < 0.5 1 2.5 2 1.8 2 0.8 215.6 < 0.5 0 < 0.5 0 1.7 2 1.8 3 0.9 218.6 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 021.6 < 0.5 0 < 0.5 0 1.2 1 < 0.5 1 < 0.5 024.6 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 2 < 0.5 030.6 < 0.5 0 < 0.5 0 4.6 2 3.4 4 0.6 233.6 < 0.5 0 < 0.5 0 2.9 2 2.1 3 < 0.5 05.2 < 0.5 0 < 0.5 0 1.7 2 2 3 < 0.5 05.7 < 0.5 0 < 0.5 0 0.8 1 2.3 3 < 0.5 16.6 < 0.5 0 < 0.5 0 < 0.5 1 1.2 1 < 0.5 27.6 < 0.5 0 < 0.5 0 1.2 2 1.6 4 < 0.5 08.6 < 0.5 0 < 0.5 0 1.2 2 0.8 3 < 0.5 09.6 < 0.5 0 < 0.5 0 1.4 2 0.9 3 < 0.5 25.7 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 08.7 < 0.5 0 < 0.5 0 0.7 1 < 0.5 0 < 0.5 09.7 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0

11.7 < 0.5 0 8.6 1 3 1 < 0.5 0 < 0.5 013.7 < 0.5 0 4.9 1 < 0.5 2 < 0.5 4 < 0.5 015.7 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 017.7 < 0.5 0 1.4 1 < 0.5 0 < 0.5 0 < 0.5 019.7 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 021.7 < 0.5 0 < 0.5 0 4.1 1 < 0.5 0 < 0.5 023.7 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 04.7 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 06.7 < 0.5 0 < 0.5 0 15.6 1 3.3 1 < 0.5 07.7 < 0.5 0 1.5 1 1.8 1 < 0.5 0 < 0.5 0

2 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 03 < 0.5 0 < 0.5 0 0.5 1 < 0.5 0 < 0.5 04 < 0.5 0 4.4 1 15.2 2 11.7 4 < 0.5 05 < 0.5 0 < 0.5 0 19.3 1 18.9 4 < 0.5 06 < 0.5 0 < 0.5 0 22.3 2 15.7 4 < 0.5 07 < 0.5 0 < 0.5 0 13.7 2 10.8 4 < 0.5 08 < 0.5 0 < 0.5 0 12.5 2 9 4 < 0.5 09 < 0.5 0 1.7 1 1.9 1 < 0.5 0 < 0.5 0

10 < 0.5 0 < 0.5 0 15.2 1 9 2 < 0.5 011 < 0.5 0 < 0.5 0 1.8 1 < 0.5 0 < 0.5 012 < 0.5 0 < 0.5 0 6.9 1 7.4 2 < 0.5 015 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 017 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 020 < 0.5 0 < 0.5 0 2.4 1 < 0.5 0 < 0.5 022 < 0.5 0 < 0.5 0 3.4 1 < 0.5 0 < 0.5 024 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 026 < 0.5 0 17.3 1 < 0.5 0 < 0.5 0 < 0.5 02 < 0.5 0 < 0.5 0 5.6 2 < 0.5 0 < 0.5 03 < 0.5 0 < 0.5 0 3.3 1 < 0.5 0 < 0.5 05 < 0.5 0 4.7 1 8.7 2 7.9 3 < 0.5 06 < 0.5 0 < 0.5 0 39.7 2 30.7 4 < 0.5 07 < 0.5 0 3.6 1 10.4 2 10.9 4 < 0.5 08 < 0.5 0 < 0.5 0 21.9 2 26.9 4 < 0.5 09 < 0.5 0 < 0.5 0 2.9 2 4.2 4 < 0.5 0

10 < 0.5 0 < 0.5 0 7 2 6 3 (1UR) < 0.5 011 < 0.5 0 < 0.5 0 1.1 1 < 0.5 0 < 0.5 012 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 013 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 015 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 013 < 0.5 0 25.5 1 < 0.5 0 < 0.5 0 < 0.5 018 < 0.5 0 < 0.5 0 0.8 1 < 0.5 0 < 0.5 020 < 0.5 0 < 0.5 0 12.7 2 7.7 3 < 0.5 0

5.7 < 0.5 0 < 0.5 0 2.9 2 2.8 4 < 0.5 09 < 0.5 0 < 0.5 0 4.3 2 2.6 3 (1UR) < 0.5 01 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 04 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0

12 < 0.5 0 13 2 < 0.5 0 < 0.5 0 < 0.5 03.7 1.7 1 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 06.1 < 0.5 0 1 1 1.4 1 < 0.5 0 < 0.5 07.1 < 0.5 0 < 0.5 0 2.5 2 1.9 4 < 0.5 08.1 < 0.5 0 < 0.5 0 < 0.5 1 < 0.5 0 < 0.5 04.8 < 0.5 0 2.4 1 1.2 1 < 0.5 0 < 0.5 05.8 < 0.5 0 < 0.5 0 1.2 1 < 0.5 0 < 0.5 06.8 < 0.5 0 < 0.5 0 2.3 1 < 0.5 0 < 0.5 07.8 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 08.1 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 09.1 < 0.5 0 2.1 1 < 0.5 0 < 0.5 0 < 0.5 0

10.1 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 03.8 < 0.5 0 1.6 1 < 0.5 0 < 0.5 0 < 0.5 09.7 < 0.5 0 12.3 1 6.1 1 14.8 3 < 0.5 0

10.7 < 0.5 0 7.2 1 7.5 1 15.5 4 < 0.5 012.7 < 0.5 0 < 0.5 0 4.4 1 9.8 4 < 0.5 014.7 < 0.5 0 < 0.5 0 2.4 1 0.5 1 < 0.5 016.7 < 0.5 0 59.8 1 7.7 1 7.6 1 < 0.5 018.7 < 0.5 0 < 0.5 0 8.7 1 4.1 1 < 0.5 012.7 < 0.5 0 3.8 1 < 0.5 0 < 0.5 0 < 0.5 016.7 < 0.5 0 < 0.5 0 2.4 1 5 3 < 0.5 09.5 < 0.5 0 1.8 1 < 0.5 0 < 0.5 0 < 0.5 0

10.5 < 0.5 0 < 0.5 0 8.5 1 < 0.5 0 < 0.5 012.5 < 0.5 0 < 0.5 0 2.3 1 < 0.5 0 < 0.5 017.5 < 0.5 0 < 0.5 0 5.8 1 2.6 1 < 0.5 0

11 < 0.5 0 < 0.5 0 11.6 1 21.1 4 < 0.5 013 < 0.5 0 < 0.5 0 9.7 1 16 4 < 0.5 015 < 0.5 0 < 0.5 0 40.5 1 76 4 7.6 118 < 0.5 0 < 0.5 0 10.9 1 16.5 4 < 0.5 020 < 0.5 0 < 0.5 1 2.1 1 8.7 3 < 0.5 0

12.7 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 016.7 < 0.5 0 < 0.5 0 3.2 1 2.7 1 < 0.5 019.7 < 0.5 0 < 0.5 0 10.1 1 7.5 2 < 0.5 010.8 < 0.5 0 < 0.5 0 3.8 1 2.5 1 < 0.5 012.8 < 0.5 0 < 0.5 0 7.8 1 14.3 3 (1UR) < 0.5 013.8 < 0.5 0 < 0.5 0 31.5 1 88.8 1 (4 UR) < 0.5 015.8 < 0.5 0 3.4 1 < 0.5 0 < 0.5 0 < 0.5 019.8 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 0 < 0.5 09.7 < 0.5 0 < 0.5 0 0.9 1 3.6 3 1.6 2

12.7 < 0.5 0 < 0.5 0 3.8 1 11.7 3 < 0.5 014.7 < 0.5 0 < 0.5 1 7.3 1 12.2 3 (1UR) < 0.5 017.7 < 0.5 0 < 0.5 0 11.7 1 20.5 3 < 0.5 014.5 < 0.5 0 < 0.5 0 11.3 1 17.9 3 < 0.5 020.8 < 0.5 0 7.9 1 < 0.5 0 < 0.5 0 < 0.5 019.7 < 0.5 0 < 0.5 0 1 1 0.5 1 < 0.5 017.8 < 0.5 0 1.6 1 < 0.5 0 < 0.5 0 < 0.5 0

Pond

C4 C5 C6 C7

Start Depth (mbwl)

C3

Pond F

Pond A

Pond B

Pond C

Pond D

Pond E

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Documents

Statistical Analysis of Reduced Sulphur Compounds...Bureau Veritas Laboratories analyzed all samples for 19 reduced sulphur compounds (Table 1), and quantified amounts of unidentified