Biogenic Interference Calculation (BIC) Index for ...

1 Alberta Peatlands=False PHC detections in peat soils surrounding an oil spill2016 RemTech Conference, Banff AlbertaBiogenic Interference Calculation (BIC) Index for Resolving False Exceedences of AB Tier-1 F3 PHC Soil Guidelines Due to Biogenic Interferences in Peat SoilsFrancine Kelly-Hooper, PhD, Soils ScientistCH2M HILL Canada??????What is the BIC Index ?Pronounced BIC like the pen Calculation for determining if Biogenic interferences have caused organic (peat) samples to falsely exceed the Alberta Tier-1, 300 mg/kg F3 PHC soil guideline. [F2/(F2+F3b)] x 100 <10% = false PHC exceedence >10% = true PHC exceedenceBIC Index Continues to Evolve After 14 Years of Research 20042016 Continuing method development2004 - 2016 Research PartnersImperial OilALS Laboratory GroupCanadian Association of Petroleum ProducersHusky EnergyAlberta Parks and Protected Areas DivisionEnvironment Canada Oil Spills Research CentreOrphan Well AssociationCanadian Geological SurveyPetroleum Technology Alliance of Canada(Village that Raised the BIC Index )Natural Sciences and Engineering Research CouncilUniversity of WaterlooSTUDY OBJECTIVES Comparison of Control Experiment Data to Field Validation DataTo determine if the BIC Index will correctly identify samples that have or have not falsely exceeded the most stringent Alberta Tier 1 F3 PHC soil guideline (300 mg/kg)

2 In all clean and contaminated soil samplesControlled Training Data SourcesData Set #1: 300-Day Crude Oil Spiked Peat PhD Experiment Clean peat and sand were spiked with crude oil and studied for Biogenic vs petrogenic carbon distributions over Set #2: 300-Day Diesel Spiked Manure PhD Experiment Compost and sand were spiked with diesel drilling invert and studied for Biogenic vs petrogenic carbon distributions over Validation Data SourcesData Set #3: Background PHC survey of 34 sites located in Alberta, BC and Newfoundland Canadian Geological Survey collected 34 background soil samples for the Biogenic vs petrogenic carbon distribution studyData Set #4: Orphan Well Association Field Validation Site The OWA collected 55 samples from a 35-year old crude oil contaminated Alberta peatland for the Biogenic vs petrogenic carbon distribution study. What are Biogenic organic compounds (BOCs)? BOCs are carbon-based compounds, which are naturally biosynthesized by living organisms.

3 BOC groups containing C, H and O include: lipids, carbohydrates, proteins and nucleic acids. BOC hydrocarbon groups containing only C and H include n-alkanes. Canadian Council of Ministers of the Environment (CCME) Reference Method for the Canada-Wide Standard (CWS) for Petroleum Hydrocarbons (PHC) in SoilMethods can produce false positives in uncontaminated organic materials ( peat, manure, etc.).The goal is to capture petroleum hydrocarbons. However, background Biogenic organic compounds are inadvertently captured as well. The problem is that the hexane and acetone solvents indiscriminately extract all carbon from petroleum and biological injectionF2, F3, F4 concentrations quantified by chromatogram integrations) ) ) ) ) ) ) )ion flowflamedetectorcapillary columncarrier gaslineVaporizer OvenFlame Ionization Detectorelectronic signalGC-FID Analysis of Sample ExtractRetention Time (minutes)0100200300pA4567891011F4 >C34F3 C16-C34F2 C10-C16 UCMD ieselF3 2000 mg/kgReported F33000 mg/kgPeatF3 1000 mg/kgDiesel-Spiked Peat GC-FID ChromatogramCarbon Numbers F1F2F4C10C16C6C34>C34F4C34F1F2C10-C16>F3 C16-C34C6-C10 Biogenic Organic Compounds( fatty acids, sterols, waxes, etc.

4 GasolineDiesel/No. 2 Fuel OilCrude OilNo. 6 Oil/Lube Oil/Heavy fuels, Tar, AsphaltsClassification of Petroleum Hydrocarbon Sources by Carbon Number RangeComparison of Background Soil Survey Results to Alberta Tier-1 Soil and Groundwater Remediation GuidelinesAlberta Tier-1 Soil Remediation Guidelines Coarse textured soil remediation guidelines may be used for organic contaminants in organic soils 34 Background Soil Samples: Alberta, BC, Newfoundland040080012001600F3 (mg/kg)Comparisons of F2, F3, F4 Concentrations to AB Tier-1 Soil Remediation Guidelines Surface Soils Natural/Agricultural/Residential/Parklan d Guidelines16 samples (47%) exceeded F3 coarse soil standard300 mg/kg050100150200F2 (mg/kg)0 samples exceeded F2 course soil standards150 mg/kg%TOC01000200030000%10%20%30%40%F4 (mg/kg)0 samples exceeded F4 course soil standards2800 mg/kg040080012001600F3 (mg/kg)16 samples (47%) exceeded F3 coarse soil standard300 mg/kg050100150200F2 (mg/kg)0 samples exceeded F2 course soil standards150 mg/kg34 Background Soil Samples: Alberta, BC, NewfoundlandComparisons of F2, F3, F4 Concentrations to AB Tier 1 Soil Remediation Guidelines Surface Soils Natural/Agricultural/Residential/Parklan d GuidelinesOnly F3 exceeded the guideline All soils with >28% TOC exceeded the F3 coarse soil standards Peat soils have >40% TOCsource.

5 Alberta Geological SurveyPeat soils cover 18% of AlbertaBut there is a light at the end of the tunnel! Biogenic Interference Calculation for Identifying False Exceedences of the AB Tier-1, F3 PHC 300 mg/kg Soil GuidelineFormulaF2 = measured F2 (C10-C16) concentration[F2/(F2+F3b)] x 100F3b = measured F3b (C22-C34) concentrationIndex Values<10% indicates that BOCs have caused falseexceedences of F3 PHC guideline>10% indicates trueexceedences of the F3 PHC guidelineNon-detectable F2 Detectable F2 Detectable F2F3a (C16-C22) and F3b (C22-C34) Distributions in Diesel and Clean PeatF3aF2 Total F3F4 Carbon NumberC16C10C22C34 Clean Peat7% F3a93% F3b11% F3b89% F3aF3b 63%F3a 37%DieselDiesel Contaminated PeatF3b(C16-C22)(C22-C34)Non-detectable F2 Detectable F2 Detectable F2F3a (C16-C22) and F3b (C22-C34) Distributions in Crude Oil and Clean PeatF2 Total F3F4 Crude + PeatCarbon NumberC16C10C22C34 Peat69% F3b31% F3aF3aF3b(C16-C22)(C22-C34)FederatedCrud e Oil 50% F3b50% F3a7% F3a93% F3b13 Crude Oil Samples% of Total F3 Concentration025507510013 Fresh Crude Oil Samples34 Background Soil Samples34 Soil Samples0255075100% of Total F3 ConcentrationF3a (C16-C22)F3b (C23-C34)F3a (C16-C22)F3b (C23-C34)

6 MedianF3b 93%F3a 7%F3b 51%F3a 49%Median123456789 10 11 12 13F2, F3, F4, F3a, F3b Carbon Distributions in PHC Products and Clean Peat F3aF3bF2F3F4 TarEngine OilCrude OilDiesel FuelPeat7% F3a93% F3bF3a 89%F3b 11%53% F3b47% F3a6% F3a94% F3b14% F3a86% F3bHigh F3aHigh F3aLow F3aLow F3aLow F3aCarbon NumberC16C10C22C34 Clean PeatDieselDiesel Spiked Peat69% 33%F2F2 = 823 mg/kgF3b = 371 mg/kgF2 = 613 mg/kgF3b = 2,816 mg/kgF2 = 10 mg/kgF3b = 1,395 mg/kgF3b= Guideline Exceedence[F2/F2+F3b] x 1001% = Guideline not Exceeded= Guideline ExceedenceExample of BIC Index for Diesel PHCsTotal F3F2 Total F3 Carbon NumberC16C10C22C34 Clean PeatF2 = 10 mg/kgF3b = 1,000 mg/kg1% Crude Oil Spiked PeatF2 = 1,000 mg/kgF3b = 2,000 mg/kg33%F3bCrude Oil F2 = 1,000 mg/kgF3b = 1,200 mg/kg45%= Guideline not Exceeded= Guideline Exceeded= Guideline Exceeded[F2/F2+F3b] x 100 Example of BIC Index for Crude Oil PHCsNoYesDoes the GC-FID chromatogram image have an obvious Unresolved Complex Mixture (UCM) petrogenic pattern?

7 NoHeavy PHCs may be present (Do not proceed with the evaluatio)Indicates falseexceedance of F3 PHC guidelineBIC Index Decision Tree for Identifying False Exceedences of AB Tier-1 F3 PHC 300 mg/kg Soil GuidelineIndicates trueexceedance of F3 PHC guidelineIs the Biogenic Interference Calculation >10%?YesPre-screening criteria: only include samples that meet these criteria1) F2 concentration is less than laboratory method detection limit (<20 mg/kg)2) F3 concentration exceeds the 300 mg/kg guideline, F4 concentration does not exceed any guidelines3) The released PHC product(s) must extend into the light F2 (C10-C16) carbon range ( diesel, crude oil, etc.)4) A qualified person must confirm that the GC-FID chromatogram does not have a heavy PHC pattern ( asphalt, bitumen, motor oil, etc.). Biogenic Interference Calculation > 10% indicates trueF3 PHC guideline exceedences<10% indicates falseF3 PHC guideline exceedencesPeat spiked with crude oil; compost spiked with diesel invert Clean soils and compostBIC Index Testing of Control Samples: Clean and Spiked Soil and CompostBiogenic Interference Calculation > 10% indicates trueF3 PHC guideline exceedences<10% indicates falseF3 PHC guideline exceedencesPeat spiked with crude oil.

8 Compost spiked with diesel invert Clean soils and compost BIC Index correctly identified trueF3 PHC guideline exceedences in all crude oil and diesel spikedsamples BIC Index correctly identified falseF3 PHC guideline exceedences in all cleansamples BIC Index Testing of Control Samples: Clean and Spiked Soil and CompostBiogenic Interference CalculationField Validations of 37 Year Old OWA Crude Oil Contaminated PeatlandPeat samples with detectableF2 and >300 mg/kg F3 concentrationsPeat samples with non-detectableF2 and >300 mg/kg F3 concentrations> 10% indicates trueF3 PHC guideline exceedences<10% indicates falseF3 PHC guideline exceedencesBiogenic Interference CalculationField Validations of 37 Year Old OWA Crude Oil Contaminated PeatlandPeat samples with detectableF2 and >300 mg/kg F3 concentrationsPeat samples with non-detectableF2 and >300 mg/kg F3 concentrations> 10% indicates trueF3 PHC guideline exceedences<10% indicates falseF3 PHC guideline exceedences All samples with >300 mg/kg F3 and non-detectable F2concentrations were identified as false PHC guideline exceedences All samples with >300 mg/kg F3 and detectable F2concentrations were identified as true PHC guideline exceedencesBIC Index

9 Statistical Probability Test ResultsThe BIC Index is a highly conservative/cautious probability of missing probability of missing falseexceedences. Next Steps? CH2M is currently expanding the BIC Index to include heavy PHCs ( asphalt, bitumen, motor oil, etc.) as