Use of GCxGC-TOFMS in litigious mixed condensate plumes: Environmental forensics case study - Multidimensional Chromatography Workshop

1. Use of GCxGC-TOFMS in litigious mixed condensate plumes: Environmental forensics case study Court D. Sandau and Lisa N. Kates Presented at Multidimensional Chromatography Workshop January 5, 2020 – Honolulu, Hawaii © 2020 Chemistry Matters Inc. Making environmental data meaningful Toluene C8 C9 C10 C11C12 C14 C16 C18 C20

2. © 2020 Chemistry Matters Inc. GCxGC in Litigation Proceedings • Daubert Standard for Admissibility – benchmark in US, applied in Canada and UK – Demonstrate that technique has been peer reviewed, published, or accepted • Ontario Ministry of Environment – three official methods GCxGC for POPs in environment Chemistry Matters Forensics Work with GCxGC • Used GCxGC-TOFMS for over 150 arson investigations since 2016 – Data accepted in 1 trial, thus far • On going litigation cases: Oil spill weathering assessment, historical gasoline spill (dissolved phase), mixed condensate plumes 2MDCW 2020 - Hawaii

3. © 2020 Chemistry Matters Inc. What is Condensate? • Complex mixture of light petroleum hydrocarbons (600-800 compounds) • Primarily used to dilute heavy crude oil for transport through pipelines • Heavy oils, especially bitumen from the oil sands in northern Alberta, use condensate to dilute the bitumen (‘Dilbit’) • Condensate is valuable; recycled and reused and is frequently transported through the North American pipeline networks 3MDCW 2020 - Hawaii Toluene C8 C9 C10 C11 C12 C14 C16 C18 C20 Gasoline Diesel Motor Oil Condensate Crude Oil Number of Carbon Atoms 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52

4. © 2020 Chemistry Matters Inc. What is the issue? 4MDCW 2020 - Hawaii • Labyrinth of pipelines, from multiple suppliers in same area makes daylighting all pipes difficult (slow and expensive) • Most recent leak blamed and assumed as source (but it has been repaired) • All lines in area have been ‘pigged’ or pressure tested – No leaks identified • Product continues to accumulate in groundwater monitoring wells (up to 80cm) What is the source of the condensate? Who should pay for cleanup?

6. © 2020 Chemistry Matters Inc. Conventional GC-FID PHC Analysis of Condensates 6 14-15 14-16 15-17 15-20 CON stream MDCW 2020 - Hawaii Total Petroleum Hydrocarbon (TPH) analysis provides little visual distinctions or data

8. © 2020 Chemistry Matters Inc. GCxGC-FID Results: Sample 14-16 8 0 1 2 3 4 5 6 7 8 0 20 40 60 80 100 120 SecondDimensionRetentionTime(min) First Dimension Retention Time (min) 18C366760 7702 - 14-16 Pr 610 peaks detected MDCW 2020 - Hawaii

9. © 2020 Chemistry Matters Inc. GCxGC-FID Results: Sample 15-17 9 620 peaks detected 0 1 2 3 4 5 6 7 8 0 20 40 60 80 100 120 SecondDimensionRetentionTime(min) First Dimension Retention Time (min) 18C366760 7703 - 15-17 Pr MDCW 2020 - Hawaii

12. © 2020 Chemistry Matters Inc. Software Limitations • Software is not yet capable of consistently exporting aligned non-targeted peak lists • Time consuming aligning peaks and data munging to get to data analysis – Limits use for forensics cases that could use non-targeted analysis 12 MDCW 2020 - Hawaii Developed stencils to capture groups of compounds and selected target compounds Alkylbenzenes Alkanes Dicyclonaphthenes Fluorenes Hopanes Indanes Naphthalenes Phenanthrenes Streranes TriAromatic Steranes Tricyclic Terpanes Cyclonaphthenes

13. © 2020 Chemistry Matters Inc. Investigation Site Data and Data Wrangling • 10 product samples from wells (collected over 2 years) – free product needed to be present in the well for sampling • 4 on-site source samples • 6 library condensate samples (for comparison) • 200 targeted stencil areas • Areas must be detected in 50% of samples • Created mixture of condensates, injected in triplicate • Triplicate must be < 25% RSD (reproducible stencils) • 101 stencil areas remained for statistical analysis, imputed missing values • Target compounds for weathering ratios were exported separately • PCA/HCA completed on % total normalized data 13 MDCW 2020 - Hawaii

19. © 2020 Chemistry Matters Inc. Multivariate Statistical Analysis of GCxGC Results 19 • 75% of variance explained in first two PCs • 14-15 (SW corner) is different from all other wells from investigation MDCW 2020 - Hawaii Library Samples Source Samples from Site Product Samples from Site Different Samples from Site

20. © 2020 Chemistry Matters Inc. 20 Reducing dimensionality using PCA and using all three PCs, 14-15 has only a 1 in 10,000 chance of being condensate from the same source as other wells. MDCW 2020 - Hawaii How Different is 14-15 from other wells?

21. © 2020 Chemistry Matters Inc. Conclusions • Free product in 14-15 is conclusively a different free product from a different release • Using multiple lines of evidence, statistics and visual aids helps communicate complex results for litigation proceedings 21 MDCW 2020 - Hawaii 14-15 14-16

22. © 2020 Chemistry Matters Inc. Future Development • Full untargeted analysis with peak alignment (use all 600-800 peaks) • Full automated weathering analysis (use all known weathering ratios) • Streamline work flow • Develop a library of condensates for reference and application for analysis • Examination of biomarkers specific to condensate for additional lines of evidence of potential sources • Forensic experimental setup and advice – library / source sample requirements (anchors for PCA/HCA) – minimum sample requirements – variability assessment (error analysis with replicates) – pooled sample of all samples to develop targeted / “non-targeted” list of compounds 22 MDCW 2020 - Hawaii

23. © 2020 Chemistry Matters Inc. 23 MDCW 2020 - Hawaii Thank you for your attention Contact Info: Chemistry Matters Inc. Court Sandau Cell: +1.403.669.8566 Email: csandau@chemistry-matters.com www.chemistry-matters.com Visit my website and sign up for email for automatic receipt of my blogs.