Characterization and Remediation of Diesel in a Fractured Rock Aquifer with a Nutrient-Flushing System

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Characterization and Remediation of Diesel in a Fractured Rock Aquifer with a Nutrient-Flushing System Presentation by David Thomson and Stefan Humphries 31-Oct-07

Authors and Collaborators Presenting Authors Stefan Humphries and David Thomson WorleyParsons Komex M. Brown, J. Armstrong, B. Reiter University of Calgary K. McLeish [Ph.D.] Dr. J. Foght Environment Canada P. Bacchus

Outline SITE BACKGROUND and CONCEPTUAL MODEL PHYSICAL HYDROGEOLOGY GEOCHEMICAL AND MICROBIOLOGICAL EVIDENCE OF NATURAL ATTENUATION NUTRIENT-AMENDED REMEDIATION SYSTEM

Site History 1982 diesel invert mud used to drill gas well; well kicked mud across lease and adjacent land 1996 - diesel impact to groundwater, drilling sump excavated 1996-2007 extensive site characterization, remedial pilot tests

Contaminant characterization Contaminant characterization Residual hydrocarbons from the former drill sump Free product and dissolved-phase impacts Typically TEH C 11 to C 27 PHC F2 (C >10 to C 16 ) Negligible salts or metals signature

Site Hydrogeology Surficial geology: Thin sand/gravel outwash or till unit (0-3 m) Bedrock: Cretaceous fractured sandstone Upper Groundwater Bearing Zone (UGBZ) 30 mbgs, within fractured sandstone unit Complex Groundwater flow Gradient to NE, fracture control mainly to SE Dissolved-phase plume stable [approx. 300 m long] Strong indication of ongoing Natural Attenuation

DUA Conceptual Hydrogeology

Importance and Relevance Domestic Use Aquifer (DUA) impacted Multiple landowners with wells Difficult hydrogeological conditions

Characterization Techniques Monitoring of 60+ piezometers Annual groundwater monitoring for routine and MNA parameters Dissolved gas sampling Passive Skimmers for product Characterization Pilot-scale grid of 12 open boreholes Aquifer pumping test Straddle packer tests Bromide tracer 4 angled coreholes Pilot testing Geophysics Core fracture mapping

Site Plan

NAPL versus Dissolved-Phase Lease Former Sump Product Plume Dissolved Plume

Fracture Control Transport Mainly to Southeast

Background Fracture-controlled system with offset plume axes Dissolved-phase and product-phase plumes are spatially and temporally stable Strong evidence of natural attenuation Geochemical indicators Stable plume

Outline SITE BACKGROUND and CONCEPTUAL MODEL PHYSICAL HYDROGEOLOGY GEOCHEMICAL AND MICROBIOLOGICAL EVIDENCE OF NATURAL ATTENUATION NUTRIENT-AMENDED REMEDIATION SYSTEM

Characterization for Remediation Pilot-scale grid of 12 open boreholes to investigate complex flow system Detailed physical characterization via: Aquifer pumping test Bromide tracer Straddle packer tests Core fracture mapping

Pilot-scale Test Area 12 closely spaced boreholes [4 cored] Oriented along major fracture azimuth Injection well Direction of plume transport ~115º Orientation of major fracture azimuth ~130º

Bedrock Coring Fracture and Oxidation Halo

Optical Televiewer Images

Fracture characterization High-angle jointing [>60 degrees] Orientation approximately 130 degrees Sub-horizontal bedding planes [<30 degrees] Matrix Permeability Permeability, porosity, grain density, pore throat radius No differences between grey and brown sandstone Permeability is orders of magnitude less than bulk rock

Pumping Test 48 hour pumping test at 5 gpm [18.9 lpm] Max. 12 cm drawdown in pilot-scale test area versus 2.5 m drawdown in PW Transmissivity estimates 7 to 30 m 2 /day 5 m Pumping Well Orientation of major fracture azimuth ~130º Direction of plume transport ~115º

Bromide Tracer Test Experimental setup Injection solution of 900L of formation water containing 325 mg/l bromide Tracer injection at 1 gpm Injection lasted approx. 90 minutes

Bromide Tracer Test Define solute transport & fracture interconnection 200 10 m 20 m 5 m 15 m Initial Br - concentration = 325 mg/l Concentration of Br - (mg/l) 150 100 50 0 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 Time (hours)

Results: 2004 Tracer Test Fastest bromide travel time approx 5 hours [for one 10m and one 20m borehole] Apparent tracer velocity 50 m/day Good results let s add nutrient next year

2005 tracer/nutrient injection Result: We couldn t find the tracer Why? Excess precipitation in 2005 led to several metres increase in groundwater elevation Likely that new flowpaths were accessed with higher water table Variable hydraulic conductivity with depth Conduct packer tests to determine variability in hydraulic conductivity with depth

Straddle Packer Tests Experimental setup One 1.5m screen with two ~1m packers Pressure transducers inside screen and above/below packers Constant-head and falling-head tests on 6 open boreholes LOWER PACKER TRANSDUCER SCREEN UPPER PACKER [not shown]

Straddle Packer Tests

Straddle Packer Results

Straddle Packer Results More than 4 orders of magnitude change in hydraulic conductivity over small vertical intervals Upper portion of saturated interval generally more conductive No definitive correlation with fracture mapping results

OUTLINE SITE BACKGROUND and CONCEPTUAL MODEL PHYSICAL HYDROGEOLOGY GEOCHEMICAL AND MICROBIOLOGICAL EVIDENCE OF NATURAL ATTENUATION NUTRIENT-AMENDED REMEDIATION SYSTEM

Natural Attenuation Indicators Aerobic Biodegradation: Oxygen = electron acceptor Anaerobic Biodegradation: Absence of oxygen Redox Sequence: NO 3- Mn 4+ Fe 3+ SO 4 2- CO 2 Mitsch and Gosselink (2000)

Zone of Depleted Dissolved Oxygen

Zone of Enriched Manganese Upgradient: Mn 2+ < 0.05 mg/l Within Plume Mn 2+ 0.05 to 3.24 mg/l Background: Mn 2+ < 0.05 mg/l

Monitoring Results: Bacterial Populations

Dissolved Gases

Lines of Evidence (EPA): Natural Attenuation Historical Geochemical Database Showing Plume Stabilization Contaminant and Geochemical Analytical Data Showing Biodegradation High to very high levels of Fe, Mn, and low levels of NO 3 within the plume Microbiological Laboratory Data High counts of Fe- and SO 4 -reducing bacteria within the plume and at the periphery microbiological activity within plume

OUTLINE SITE BACKGROUND and CONCEPTUAL MODEL PHYSICAL HYDROGEOLOGY GEOCHEMICAL AND MICROBIOLOGICAL EVIDENCE OF NATURAL ATTENUATION NUTRIENT-AMENDED REMEDIATION SYSTEM

Remediation limitations Traditional hydrocarbon recovery methods limited by: Depth of impacts Complex fractured media Discontinuous distribution of hydrocarbons Low volatility of contaminant

Enhanced Biodegradation Natural biodegradation confirmed in field Laboratory bench-scale biodegradation experiments Nutrient amendment experiments at University of Alberta Cross, Biggar et al. (J. Env. Eng. manuscript)

Lab Scale Microcosms Anaerobic TEH (C 11 to C 27 ) Degradation Microcosm Temperature (deg C) Estimated Half- Life (yrs) No amendment 10 3.8 Sulphate amended 10 3.2 Nitrate amended 10 1.9 Nutrient mix amended 10 1.2

Nutrient Amendment Proposal Parameter Target (mg/l) Drinking Water Guideline (mg/l) Nitrate (NO3 as N) 8 10 Sulphate (SO4) 200 500 Phosphate (PO4 as P) 3 - - Ammonium (NH4) 10 - - Potassium (K) 30 - - Chloride (Cl) 20 250

Nutrient Flush Planning Steps Permission from AENV Several conditions related to input values to DUA Hydraulic controls to ensure no uncontrolled migration (i.e., forced gradient best) Tracer & pilot testing Confirm flowpaths & velocity by conservative tracer Ensure quality control of nutrient solution (i.e., impurities in commercial fertilizers)

Site Plan

Infiltration Gallery

DUA Infiltration

Site Plan

Site Plan

Well Pairs

Process Design

Collection Network

Pictures from the field

Remediation Summary Nutrient Amendment works at the lab scale Modelled estimate 13 wells & 2 infiltration galleries Outer Perimeter Wells and 2 nd infiltration gallery for hydraulic control of plume Inner Well Pairs attempt to limit smearing of free phase plume GW Treatment train Remove HC & amend with NO3, SO4, micronutrients, dissolved oxygen Forced gradient nutrient circulation for in-situ treatment of dissolved phase HC Concentration gradient will assist with matrix diffusion Free product skimming near pumped wells

Conclusions Fractured rock sites require extensive characterization (standard & unconventional) Detailed hydrogeological model is key Difficult conditions (non-volatile hydrocarbons, fractures, domestic use aquifer) require innovation Nutrient amendments a promising alternative for in-situ treatment Full scale system is currently being constructed

QUESTIONS?

Dissolved Gases