INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Enhanced Anaerobic
Biodegradation of a
Refinery Benzene
Groundwater PlumeRobert (Rory) S. Johnston, PEMichael Eberle
SAWEA CONFERENCE DECEMBER 2007
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Refinery History1913 – 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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
SMRC Refinery, St Marys, WVSite
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Cross Section C-C’
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
AOC 2 Residual Source Areas
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
OW-7/MW-18 Area, BETX Concentrations vs. Time
0.00
10.00
20.00
30.00
40.00
50.00
60.00
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)
Co
ncen
trati
on
(p
pm
v) Ethylbenzene
Toluene
Xylenes
Benzene
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Initial Evaluation
Turn Off SVE System
Evaluate Groundwater
Evaluate Large Scale (Full Refinery) Bioventing
Understand Complex Geology through Gamma Logging
of Extractions Wells
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Section C-C’
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Site-Wide Groundwater Results BETX vs. SO4
October 2004
0
20
40
60
80
100
120
0 2000 4000 6000 8000 10000 12000
Benzene Concentration (ug/l)
SO
4 C
on
cen
trati
on
(m
g/l)
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Benzene Plume Map
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
SVEB System Overview
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Air Emissions and Remediation Schematic
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Microbial Respiration /Activity
0
5
10
15
20
0 500 1000 1500 2000 2500
CO
2 &
O2 (
%) )
O2 CO2
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
O=C=O
O
H HCatalytic Oxidizer
Reaction Inside Catalytic Oxidizer
VOCs, Benzene, etc. + O2 CO2 + H2O
900o
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Overview of SVEB Piping
Layout
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
SVEB System Output
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
3/19/07 4/8/07 4/28/07 5/18/07 6/7/07 6/27/07 7/17/07 8/6/07 8/26/07 9/15/07 10/5/07
Ben
zen
e (l
bs/
hr)
Maximum Permitted Emission Rate
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Radius of Influence from SVEB
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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 6th Streets
Estimated Completion Date Summer 2008
System will be Converted to a Barometric Pumping Bioventing System
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
SULFATE ADDITION
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
St. Marys Refinery Sulfate Addition
to Ground Water
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Refinery Plume Map
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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.
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
Preliminary Sulfate Addition ResultsEAB Pilot I and II - Progress Monitoring
0
0.01
0.02
0.03
0.04
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
Ben
zen
e (
mm
ole
s/l
)
0
1
2
3
4
5
6
7
8
9
SO
4 (m
mo
les/l)
Benzene Sulfate
Sulfate Amendments
MgSO4
3,000 ug/l
300 ug/l
20,000 lbs 65,000 lbs2,000 lbs
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
Summary of Combined Remedial
Approaches with Sulfate Injections
2004 – October 2007
INDEPENDENT ENVIRONMENTAL ENGINEERS, SCIENTISTS AND CONSULTANTS
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
