Assessment of Variability in Flux Chamber-based Soil CO 2 Efflux Measurements at Petroleum Remediation Sites
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1 Assessment of Variability in Flux Chamber-based Soil CO 2 Efflux Measurements at Petroleum Remediation Sites Ellen Porter- CH2M HILL, Calgary Remediation Technologist October 17, 2014 Innovation that Solves Complex Local Challenges, Worldwide
2 Outline Why Perform Efflux Assessments? Technology Data Quality Uncertainties Temporal and Barometric Variability Site Geology and Ground Surface Cover Comparisons Hydrocarbon Removal, Monitoring and Mass Budgeting Efficiency and Cost Conclusions 2
3 Introduction Gas exchange takes place between soil and atmosphere Downward movement of oxygen (O 2 ) and upward venting of CO 2 Affected by factors that change temperature/pressure and moisture CO 2 is derived from respiration processes occurring in both shallow aerobic, and deeper anaerobic, ecosystems 3
4 Why Perform Efflux Assessment Semi-quantitatively delineate source zones - free phase non-aqueous phase liquid (NAPL) Estimate site wide biodegradation Better estimation of hydrocarbon removal rates In lieu of groundwater natural attenuation indicator parameters (NAIPs) analysis Biodegradation vs mechanical extraction systems Monitored natural attenuation (MNA) Economical 4
5 Soil Flux System (LI-COR, Inc.) Equipment Ground surface collar Vented bellows-controlled flux chamber with rubber gasket Application software, analyzer unit (infrared gas analyzer) and pump 5
6 LI-COR Survey Procedures Theory The rate of change of CO 2 concentration inside a vented flux chamber is equated to flux Uses early time data before chamber accumulation effects occur Deadband = 20 seconds Observation Rate = 90 seconds Post-purge = 30 seconds Minimum Number of Measurements = 3 * Cdry (ppm) Regression Plot Measured 1st Order Exp Slope Time (s)
7 Fall 2013 and Summer 2014 Multisite CO 2 Survey 6 sites, 21 rounds of efflux monitoring, 163 locations, 1,529 measurements Site conditions from active gas plant to remote maintenance yard containing a variety of hydrocarbons Site Name Date(s) CO 2 Survey Performed Type of Product Release Age Subsurface Soil Type Estimated Size of LNAPL Footprint (ha) Yukon September, 2013 June, 2014 TransCanada 1 September - October, 2013 Crude, Diesel, July - August, 2014 NGLs Ferrier October, 2013 Crude Since 1971 Ferrier September, 2013 NGLs, LPG Since 1968 Arctic Diesel Since 1960s Fill, sand, and gravel Since 1966 Fill, silty sand 0.50 Clay underlain by sandstone bedrock Sand underlain by sandstone bedrock Ferrier September, 2013 Waste Oil Since 1960s Fill, silty sand, and gravel Ferrier October, 2013 Crude, NGLs Since Aug 2006 Silt and clay underlain by sandstone bedrock 5.5 7
8 Background Correction Measurements averaged at each location for each monitoring round 55 background locations 108 locations over the LNAPL footprint NSZD-derived CO 2 efflux (q CO2 -NSZD) q CO2 -NSZD = q CO2 -Total q CO2 -Background Correction made for each monitoring round which spanned 3-5 hours time (15-30 collars) 8
9 Background CO 2 Contribution Grass Location Background ranged from 0.6 to 5.3 µmol/m 2 /s (average 1.3 µmol/m 2 /s) 2013 Higher Background Background ranged from 0.8 to 5.8 µmol/m 2 /s (average 3.2 µmol/m 2 /s) 2014 Gravel Location Lower Background 9
10 Total CO 2 Efflux Measurement Precision Across all sites, the std dev ranged from 3.1% to 30% of the average efflux (mean of 16%) in 2013; 9% to 13% of the average efflux (mean of 11%) in 2014 ~0.3 µmol/m 2 /s on overall average of 2.1 µmol/m 2 /s total CO 2 efflux ~0.3 µmol/m 2 /s on overall average of 2.8 µmol/m 2 /s total CO 2 efflux
11 Range of Total Efflux Field replicate measurement results within ~0.25 µmol/m 2 /s in 2013; ~7.2 µmol/m 2 /s in 2014 Corrected efflux ranged from 0 to 10.5 µmol/m 2 /s (average 1.27 µmol/m 2 /s) 11
12 Total CO 2 Efflux Multiday Measurements Day 1 Sun, 9-15 o C, <5 km/h wind Day 2 Sun, 9-11 o C, up to 30 km/h wind Day 5 Rain, 3-6 o C Day 7 Light rain, 4-7 o C, up to 15 km/h wind Day 12 Sun, o C, up to 45 km/h wind Day 15 Sun, o C, up to 20 km/h wind Day 1 Rain overnight, sun, rain, and thunder, o C, up to 18 km/h wind Day 3 Fog, sun, o C, up to 15 km/h wind Day 10 Rain overnight, sun, o C, up to 12 km/h wind Average variation in total CO 2 efflux over two week period was 1.1 µmol/m 2 /s (2013) and 1.6 µmol/m 2 /s (2014) at all locations with multiple day measurements 12
13 Corrected CO 2 Efflux Multiday Measurements Day 1 Sun, 9-15 o C, <5 km/h wind Day 2 Sun, 9-11 o C, up to 30 km/h wind Day 5 Rain, 3-6 o C Day 7 Light rain, 4-7 o C, up to 15 km/h wind Day 12 Sun, o C, up to 45 km/h wind Day 15 Sun, o C, up to 20 km/h wind Day 1 Rain overnight, sun, rain, and thunder, o C, up to 18 km/h wind Day 3 Fog, sun, o C, up to 15 km/h wind Day 10 Rain overnight, sun, o C, up to 12 km/h wind Similar average variation as total CO 2 efflux, 1.0 µmol/m 2 /s (2013), 1.2 µmol/m 2 /s (2014) Suggests combination of subsurface changes occurred to cause variability 13
14 Source Zone Depletion Rates 2C 8 H O 2 --> 16CO H 2 O Site Name Type of Ground Cover Average Background CO 2 Efflux (µmol/m 2 /s) Avg. Corrected CO 2 Efflux (µmol/m 2 /s) Average LNAPL Degradation Rate (g/m 2 /d) Yukon Grass Ferrier Grass TransCanada Grass Ferrier Grass Ferrier Grass Yukon Grass TransCanada Grass Ferrier Grass
15 Source Zone Depletion Rates 2C 8 H O 2 --> 16CO H 2 O Site Name Type of Ground Cover Average Background CO 2 Efflux (µmol/m 2 /s) Avg. Corrected CO 2 Efflux (µmol/m 2 /s) Average LNAPL Degradation Rate (g/m 2 /d) TransCanada Gravel Yukon Gravel TransCanada Gravel Ferrier Gravel Yukon Gravel Ferrier Gravel Ferrier Gravel Ferrier Gravel
16 Fall 2013 and Summer 2014 Multisite CO 2 Survey 6 sites, 21 rounds of efflux monitoring, 163 locations, 1,529 measurements Site conditions from active gas plant to remote maintenance yard containing a variety of hydrocarbons Site Name Date(s) CO 2 Survey Performed Release Age Estimated Size of LNAPL Footprint (ha) Estimated Sitewide NSZF Rate (kg/yr) September, Yukon Since 1960s June, TransCanada 1 September - October, ,900 Since July - August, ,842 Ferrier October, 2013 Since ,963 Ferrier September, 2013 Since ,130 Ferrier September, 2013 Since 1960s 1.3 8,307 Ferrier October, 2013 Since Aug ,674 16
17 Ground Surface Temperature Discernible effect on total CO 2 efflux 2013 Dampened effect of temperature to a level comparable to measurement variability (<0.6 µmol/m 2 /s)
18 Pressure, Moisture, and Wind Indiscernible effect with pressure and moisture content Wind is a non-issue if instrument rubber gasket is in good shape and set correctly to isolate chamber from wind effects Tortuous chamber vent prevents wind influencing measurements Chamber Vent 18
19 LI-COR and Groundwater Monitoring TransCanada Rate of Removal (kg/yr) LI-COR MPE Rate of Removal (kg/yr) Year Yukon Year LI-COR NAIP Analysis 19
20 Efficiency and Cost 30 LI-COR locations v s 30 groundwater samples LI-COR Current GW Sampling Time 3-5 hrs/round 3 days/round Cost ~$1800 a ~$ $4000 b Field Staff Required 1 2 a First month - ~$1800, subsequent months - ~$1000 b NAIPs only nitrate/nitrite, sulphate/sulphite, alkalinity, ferrous iron, dissolved methane, dissolved oxygen and dissolved carbon dioxide. 20
21 Conclusions CO 2 Efflux Assessment Semi-quantitatively delineate free phase NAPL More realistic estimates of hydrocarbon removal rates through biodegradation LI-COR precision observed: ~ +/- 0.3 µmol/m 2 /s (total efflux) Time and cost efficient Fewer field staff required Variability Ecosystem-related (background) contributions to total CO 2 efflux are generally small ~ µmol/m 2 /s Ambient air temperature showed most significant effects to total efflux 21
22 Managing Variability Standard installation protocol 6 Standard weighted tamping device for re-compaction of soil to natural conditions Wait at least 4 hours after a precipitation event Maintain a 1.5-m distance from ground surface disturbances Regular practice of duplicate efflux systems approximately 1 m Create a detailed method for background corrections 22
23 Conclusions Further work Next step assess effects of subsurface changes on efflux (i.e., seasonality) Data analysis underway Investigate effects of depth Use at more sites across Canada Recognize CO 2 efflux monitoring as a method for monitoring NA and NSZD 23
24 Thanks to Co-Authors Darcy Bye TransCanada PipeLines Limited Ruth Hall Environment Yukon Amy Jimmo CH2M HILL, Edmonton Tom Palaia CH2M HILL, Denver 24
25 Thank you for Your Time! Innovation that Solves Complex Local Challenges, Worldwide
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