Using Humalite-Derived Humic Products to Mobilize Soil-Adsorbed

Hydrocarbons and Enhance Natural Attenuation

October 15, 2004

Trenton M. Parks, Ph.D., P.Chem.Stantec Consulting Ltd.

The Problem

• Old oil sites

The Problem

• Old oil sites

• Light-end hydrocarbons have “gone away”

The Problem

• Old oil sites

• Light-end hydrocarbons have “gone away”

• Heavier-end hydrocarbons are sorbed to soils

The Problem

• Low levels of HCs in groundwater

The Problem

• Low levels of HCs in groundwater

• High levels of HCs in soil

The Problem

• Low levels of HCs in groundwater

• High levels of HCs in soil

• Can’t get site closure

The Problem

• Groundwater remediation methods are ineffective

The Problem

• Groundwater remediation methods are ineffective

• Natural attenuation is very, very slow

The Problem

• Groundwater remediation methods are ineffective

• Natural attenuation is very, very slow

• “Dig ‘n’ Dump” has been the traditional method of dealing with the problem

The Problem

• “Dig ‘n’ Dump” is simple

The Problem

• “Dig ‘n’ Dump” is simple

• “Dig ‘n’ Dump” is expensive

The Solution?

• Controlled mobilization of HCs

The Solution?

• Controlled mobilization of HCs

• Allows ex-situ treatment of groundwater

The Solution?

• Controlled mobilization of HCs

• Allows ex-situ treatment of groundwater

• Improves the rate of natural attenuation

The Solution?

• Surfactants

The Solution?

• Surfactants

• Humic products

Humic Products

Humic Products

• Humic acid

Humic Products

• Humic acid

• Humate

Humic Products

• Humic acid

• Humate

• Humalite

Humic Products

• Naturally occurring

Humic Products

• Naturally occurring

• Highly oxidized

Humic Products

• Naturally occurring

• Highly oxidized

• Organic material

Humic Products

• Naturally occurring

• Highly oxidized

• Organic material

• Found adjacent to sub-bituminous coal

Humic Products

• “Water soluble”

Humic Products

• “Water soluble”

• Actually colloidal

Humic Products

• “Water soluble”

• Actually colloidal

• Particles 1 nanometer to 1 micron

Humic Products

• Mobilizes bound HCs by providing sites for preferential adsorbance

Humic Products

• Mobilizes bound HCs by providing sites for preferential adsorbance

• HCs are brought into “solution”

Humic Products

• Surfactants

Humic Products

• Surfactants

• Humics

o Naturally occurring

Humic Products

• Surfactants

• Humics

o Naturally occurring

o Non-toxic

Humic Products

• Surfactants

• Humics

o Naturally occurring

o Non-toxic

o Inexpensive

Pilot Study

• Devon Canada Corporation’s Foothills #9 Battery Site

Pilot Study

• Devon Canada Corporation’s Foothills #9 Battery Site

• Abandoned battery site

Pilot Study

• Devon Canada Corporation’s Foothills #9 Battery Site

• Abandoned battery site

• Well drilled in 1944

Pilot Study

Pilot Study

• Sandy loam of glaciofluvial origin 3.0 m thick

Pilot Study

• Sandy loam of glaciofluvial origin 3.0 m thick

• Clay till underlying

Pilot Study

• Sandy loam of glaciofluvial origin 3.0 m thick

• Clay till underlying

• Groundwater is 2.2 to 2.9 mbgs

Pilot Study

• Sandy loam of glaciofluvial origin 3.0 m thick

• Clay till underlying

• Groundwater is 2.2 to 2.9 mbgs

• Hydraulic conductivities of 10-5 to 10-3 m/s

Pilot Study

Pilot Study

Pilot Study – First Injection

• First injection on 3 August 2004

Pilot Study – First Injection

• First injection on 3 August 2004

• 3.75 kg of Dry Soluble 80

Pilot Study – First Injection

• First injection on 3 August 2004

• 3.75 kg of Dry Soluble 80

• 115 L of distilled water

Pilot Study – First Injection

Pilot Study – First Injection

Pilot Study – First Injection

Pilot Study – First Injection

• Solution of approximately 33.1 g/L

Pilot Study – First Injection

• Solution of approximately 33.1 g/L

• Approximately 40 L poured into each of 3 injection wells

Pilot Study – First Injection

• Solution of approximately 33.1 g/L

• Approximately 40 L poured into each of 3 injection wells

• Rate of approximately 3.33 L/s

Pilot Study – First Injection

• Weekly – field screening for pH, temperature, specific conductance, EC, TDS, DO and ORP

Pilot Study – First Injection

• Weekly – field screening for pH, temperature, specific conductance, EC, TDS, DO and ORP

• Weekly at closest wells – laboratory analysis for TEH

Pilot Study – First Injection

• Weekly – field screening for pH, temperature, specific conductance, EC, TDS, DO and ORP

• Weekly at closest wells – laboratory analysis for TEH

• Weekly at “anaerobic” wells – laboratory analysis for ferric/ferrous, nitrate/nitrite, and sulfate/sulfite speciation

Pilot Study – First Injection

• Weekly – field screening for pH, temperature, specific conductance, EC, TDS, DO and ORP

• Weekly at closest wells – laboratory analysis for TEH

• Weekly at “anaerobic” wells – laboratory analysis for ferric/ferrous, nitrate/nitrite, and sulfate/sulfite speciation

• Monthly – laboratory analysis for routine parameters, major ions and dissolved metals, and hydrocarbons (BTEX, F1, F2, TEH)

Pilot Study – First Injection

• What happened?

Pilot Study – First Injection

• What happened?

• After 28 days…

Pilot Study – First Injection

• What happened?

• After 28 days…

• …Not much

Pilot Study – First Injection

Pilot Study – 2nd Injection

• Second injection on 8 September 2004

Pilot Study – 2nd Injection

• Second injection on 8 September 2004

• Three batches of 6.35 kg of Dry Soluble 80

Pilot Study – 2nd Injection

• Second injection on 8 September 2004

• Three batches of 6.35 kg of Dry Soluble 80

• 189 L of distilled water per batch

Pilot Study – 2nd Injection

• Solutions of approximately 33.6 g/L

Pilot Study – 2nd Injection

• Solutions of approximately 33.6 g/L

• 189 L poured into each of 3 injection wells

Pilot Study – 2nd Injection

• Solutions of approximately 33.6 g/L

• 189 L poured into each of 3 injection wells

• Rate of approximately 1 L/min

2nd Injection

Pilot Study – 2nd Injection

Pilot Study – 2nd Injection

Pilot Study – 2nd Injection

Pilot Study – 2nd Injection

• What happened?

Pilot Study – 2nd Injection

• What happened?

• After 6 days…

Pilot Study – 2nd Injection

• What happened?

• After 6 days…

• …humic product was visible in all of the wells!

Pilot Study – 2nd Injection

• 04-MW19 – farthest downgradient monitoring well

o Initial (pre-injection) TEH = 4.5 mg/L

Pilot Study – 2nd Injection

• 04-MW19 – farthest downgradient monitoring well

o Initial (pre-injection) TEH = 4.5 mg/L

o One week after second injection = 18 mg/L

Pilot Study – 2nd Injection

• 04-MW19 – farthest downgradient monitoring well

• Additional evidence that the humic product is effective in mobilizing sorbed HCs

o Initial (pre-injection) TEH = 4.5 mg/L

o One week after second injection = 18 mg/L

Recent Results

• Field parameters using a flow cell and mini-purging

Recent Results

• Field parameters using a flow cell and mini-purging

• Monthly laboratory analytical results

Future Work

• Biodegradation processes

Future Work

• Biodegradation processes

• Collection of subsurface soil samples

Acknowledgements

• Devon Canada Corporation – Tim Robbie

• Cathy Main, Mike LaPlante, Karen Hincks

• Dr. Dale VanStempvoort – National Water Research Institute

• Black Earth Humates Ltd.