Enhanced Anaerobic Biodegradation of a Refinery Benzene Groundwater Plume Robert (Rory) S. Johnston, PE Michael Eberle SAWEA CONFERENCE DECEMBER 2007
Presentation Outline Go With the Flow Anaerobic Process Naturally Occurring Compounds Degraded by Sulfate Reducing Bacteria (SRB) Effective When Coupled with Mass Reduction Case Study-Enhanced Anaerobic Degradation by SRB Large Refinery Site Additional Applications for MTBE Potential Applications - Remediating Dissolved Metal Plumes SRB - Friends or Foes Enhances the Attenuation of Hydrocarbon & Oxygenate Plumes Inhibits the Attenuation of Halogenated Plumes
Refinery History 1913 Refinery constructed 1987 Original Owner sells refinery 1988 New Owner files for bankruptcy, refining ceases 1989 In the interim, another Operator leases facility, starts jet fuel production 1991 New Owner buys refinery out of Bankruptcy Court, crude refining restarts 1993 Owner stops refining, lays off most workforce 1996 Owner uses facility for bulk storage and distribution 1997 Interim remediation started using Dual Phase Extraction (DPE) 1997 Regulatory Agency issues Owner an AOC under Section 7003 of RCRA 2004 Regulator requests Owner to address impacts at offsite pipeline 2004 New Consultant Retained-Develop Exit Strategy and Expedited Program 2005 Interim Dual Phase Extraction (DPE) started at offsite pipeline 2005 Design of Expedited Program 2006 Bioventing (SVEB) and Sulfate Pilot testing started on Refinery 2007 Full Scale SVEB initiated at refinery-second Pilot test on sulfate conducted
Site SMRC Refinery, St Marys, WV
Major AOCs and Contaminants Central Plant Area (AOC -2) BTEX, LNAPL, MTBE & As Bluff Area 2 landfilss reported to contain listed waste Offsite Area Benzene & MTBE Pipeline Area LNAPL and BETX
Refinery Operations Impacts Source of impacts: refinery processes including sewers, piping, storage tanks, and process units Impacted soils: confined within the central refinery and pipeline areas Groundwater flow: impacted groundwater extends approximately 300 feet to the west and is confined within a narrow region due to the natural groundwater gradient and natural attenuation processes However past groundwater flow influenced by town water wells to the north
General Site Conditions GW flow direction is towards Ohio River Three layers of groundwater flow shallow (low permeability), intermediate and deep (most permeable)-delineation issues near Ohio River Offsite groundwater impacts in deeper layers Onsite groundwater impacts in all three layers Onsite soil impacts shallow and deep Pipeline and Barge area groundwater and shallow soil impacts associated with pipeline releases
Cross Section C-C
Initial Remedial Actions 1987-2004 Impacted Soils Removed 1987 Almost 1 million pounds (470 tons) of petroleum impacted soils removed Known Light Non-Aqueous Phase Liquid (LNAPL) Removed 1993-1994: Approximately 36,000 gallons of total fluids recovered 1995-2003: More than 1,800 gallons of oil recovered Satisfied Agency remediation requirements Localized Soil Vapor Extraction (SVE) operations 1996-2004: Approximately 480,000 pounds of hydrocarbons removed from soil Approximately 2 times as much (960,000 lbs.) estimated to have been degraded by naturally occurring microorganisms at the site Benzene Groundwater Concentration Reduced by 99% in these zones Satisfied Agency remediation requirements
AOC 2 Residual Source Areas
Observations of SVE System Operating for 6-8 years No Optimization Influent Streams flat Need new approach for Residual Hydrocarbon Removal Must also deal with Offsite Plume
Concentration (ppmv) OW-7/MW-18 Area, BETX Concentrations vs. Time 60.00 50.00 40.00 30.00 Ethylbenzene Toluene Xylenes Benzene 20.00 10.00 0.00 7/20/1995 12/1/1996 4/15/1998 8/28/1999 1/9/2001 5/24/2002 10/6/2003 2/17/2005 Date (MM/DD/YYYY)
Initial Evaluation Turn Off SVE System Evaluate Groundwater Evaluate Large Scale (Full Refinery) Bioventing Understand Complex Geology through Gamma Logging of Extractions Wells
Section C-C
SO4 Concentration (mg/l) Site-Wide Groundwater Results BETX vs. SO4 October 2004 120 100 80 60 40 20 0 0 2000 4000 6000 8000 10000 12000 Benzene Concentration (ug/l)
Benzene Plume Map
Refinery Remediation Strategy Remove hydrocarbons from soil Remediate residual LNAPL pockets (Dual Phase/SVE) Biodegrade hydrocarbons dissolved in groundwater Selected Technologies: Soil Vapor Extraction /Bio-venting (SVEB) Sulfate Addition Satisfy environmental obligations
SVEB System Overview
Air Emissions and Remediation Schematic
Microbial Respiration /Activity 20 CO2 & O2 (%)) 15 10 5 0 0 500 1000 1500 2000 2500 O2 CO2
Reaction Inside Catalytic Oxidizer 900 o O=C=O Catalytic Oxidizer H O H VOCs, Benzene, etc. + O 2 CO 2 + H 2 O
Preparation for Next Phase of Refinery Remediation Installed 71 Monitoring Wells, and 106 Geo-probes Collected and analyzed approximately 1,500 groundwater and more than 500 soil samples Successful bio-venting pilot test Conducted feasibility studies of piping routing Evaluated feasibility of Sulfate Injections
SVEB Construction Well Installation Completed 110 Extraction Wells Installed Injection/extraction lines Completed December 2006 2 Miles of Piping Installed Equipment Installation Completed December 2006 System Startup Completed February/March 2007 Full Operations March 2007
Overview of SVEB Piping Layout
Benzene (lbs/hr) SVEB System Output 0.07 Maximum Permitted Emission Rate 0.06 0.05 0.04 0.03 0.02 0.01 0 3/19/07 4/8/07 4/28/07 5/18/07 INDEPENDENT 6/7/07 ENVIRONMENTAL 6/27/07 7/17/07 ENGINEERS, 8/6/07 SCIENTISTS AND 8/26/07 CONSULTANTS 9/15/07 10/5/07
Radius of Influence from SVEB
SVEB Remedial Progress Residual Source is approximately 50% Remediated Greater than 95% operational time Actual Area Influenced 3x Further and Projected Vacuum is 10x Higher than Design Estimate Identified and Recovered Natural Gas from a Gas Leak discovered near Washington and 6 th Streets Estimated Completion Date Summer 2008 System will be Converted to a Barometric Pumping Bioventing System
SULFATE ADDITION
St. Marys Refinery Sulfate Addition to Ground Water
Refinery Plume Map
Phase II Preliminary Results 4 Million Gallons of Water Recirculated 65,000 lbs of MgSO4 Approximately 70% of the SO4 was Utilized 75% of the Plume Width is being Remediaited 70% Reduction in Benzene Conc.
Benzene (mmoles/l) SO4 (mmoles/l) 0.04 EAB Pilot I and II - Progress Monitoring Preliminary Sulfate Addition Results 3,000 ug/l 9 2,000 lbs 20,000 lbs 65,000 lbs 8 0.03 7 Sulfate Amendments MgSO4 6 5 0.02 4 3 0.01 2 0 0 2/17/2005 5/28/2005 9/5/2005 12/14/2005 3/24/2006 7/2/2006 10/10/2006 1/18/2007 4/28/2007 8/6/2007 11/14/2007 Benzene Sulfate 300 ug/l 1
Sulfate Amendment Schedule Phase I permits received - May 2005 Phase I pilot test completed - September 2005 Additional system components installed/permits received - September 2006 Phase II testing initiated - October 2006 System Expanded May 2007 Phase II testing will be completed December 2007 Full-Scale Installation and Operation Spring 2008
Summary of Combined Remedial Approaches with Sulfate Injections 2004 October 2007 Completed Phase I and Initiated Phase II of Sulfate Addition Pilot Tests Designed and Installed Full-Scale SVE/Bioventing System Operated Full-Scale SVE/Bioventing System for 8 months Completed Remediation of POTW Source Area
SRB- Friends or Foes? Enhances the Attenuation of Hydrocarbon & Oxygenate Plumes Reliable Technology if Naturally Occurring Conditions are Appropriate Maybe Limited by Nutrient and Co-substrate Availability Inhibits the Attenuation of Halogenated Plumes SRB Out-Compete Dehalogenators for Limited Nutrients Sulfate is and Electron Acceptor and Must Be Reduced Prior to Reducing Halogenated Compounds