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Innovative Bioremediation Demonstrations of Petroleum Contaminated Sites in Poland and US. PERF Meeting at LBNL March 10,1999. Terry C. Hazen Earth Sciences Division Lawrence Berkeley National Laboratory University of California [email protected] www-esd.lbl.gov/ERT/ert.html.

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slide1

Innovative Bioremediation Demonstrations of Petroleum Contaminated Sites in Poland and US.PERF Meeting at LBNL March 10,1999

Terry C. Hazen

Earth Sciences Division

Lawrence Berkeley National Laboratory

University of California

[email protected]

www-esd.lbl.gov/ERT/ert.html

u s department of energy poland initiative
U.S. Department of Energy-Poland Initiative
  • The mission of U.S. DOE and the Polish Institute for Ecology of Industrial Areas (IETU) Katowice, Poland partnership is to establish the Risk Abatement Center for Eastern and Central Europe (RACE).
  • IETU/RACE in cooperation with the U.S. team will demonstrate the U.S. DOE process for investigation, evaluation and remediation of a hazardous waste site.
  • 1995-7: Characterization and demo of biosparging/bioventing bioremediation of oil refinery waste lagoon at the Czechowice Oil Refinery.
  • A goal is to provide a mechanism for the transfer of those techniques and technologies used in the demonstration to Poland and other countries in the region.
  • The Initiative will provide for the advancement of EM technologies for use at other DOE facilities and promote commercial development between U.S. and Polish environmental firms.
objectives
OBJECTIVES
  • Demonstrate Cost Effective Remediation of Czechowice Oil Refinery (COF) Lagoon by:
    • Reducing the risks associated with both the soil and lagoon water. (Risk Assesment must determine an acceptable level.)
    • Remediate to a level which will support a green zone (i.e. Grow grass.)
  • Train and Transfer Bioremediation technology to the IETU, Poland, and RACE.
  • Evaluate the technology deployed for effectiveness and cost efficiency, eg. compare passive vs. active aeration.
  • Transfer technology gleaned (isolates) to DOE sites.
biodegradation rates bioventing vs prepared bed
Biodegradation Rates: Bioventing vs. Prepared Bed

Prepared Bed Bioventing

  • Various (Bartha, 1986) 52-641
  • SRS 10-107 10-65
  • Italy (biopile - crude) 60
  • Hill AFB, Utah 10
  • Tyndall AFB, Florida 2-20
  • The Netherlands 2-5
  • The Netherlands 8
  • Patuxent River NAS, Maryland 3
  • Fallon NAS, Nevada 5
  • Eicklson AFB, Alaska 1-10
  • Kenai, Alaska 21
  • Tinker AFB, Oklahoma 2.7-18

*all values in mg/kg/day

czechowice oil refinery
Czechowice Oil Refinery
  • The Silesian Refinery Works, known as the Czechowice Oil Refinery started in 1896 when the Schodnica refinery was built.
  • A second refinery was built in 1902 by the Vacuum Oil Company which was owned by the Socony Vacuum Oil Company Inc., New York USA.
  • The first distillation unit was built in 1931 by Foster Wheeler.
  • The refinery was bombed by the Allies in 1943 and partially rebuilt by the Germans during the war.
  • Polish engineers and workers finished the restoration shortly after the war and production resumed in 1946.
  • Cresol was refined into grease with a capacity of 25,000 tons/yr.
  • Between 1959 and 1962 capacity increased to 500,000 tons/yr.
  • Thallic and turpentine oils processing was added in 1985.
  • Today’s free market products include ethyl gasoline, engine oil , fuel oil, paraffins, asphalts, and special oils.
treatability test results
Treatability Test Results
  • Indigenous microbes that degrade contaminants are present
  • Microbes present can be stimulated to degrade contaminants at high rate (90% reduction of TPH in <21 days) - IETU and SRTC
  • 36 Low pH (<3) organisms that degrade contaminants have been isolated (unique atributes make them patentable)
  • High clay content of some soils shows even higher stimulation than low clay content soils
  • Biodegradation of contaminants is correlated with increased CO2 production
  • pH adjustment is not as important for stimulation as nutrients (N&P)
  • Local dolomite can be used to increase pH
  • Local wood chips can be used to provide bulking agent
  • 36 isolates of unique acidophilic PAH degraders undergoing identification and molecular characterization in FY98.
slide11
Precipitation (and Oxygen)

passive aeration

Wastewater

Treatment

Baroball

Fertilizer

(N & P)

Volatilization

Evaporation

Outside

Wall to be

Lowered

Surface

run-off

Top Soil

CO2

H2O

Methanotrophic

bacteria

Storm Drain

Subsurface

irrigation

Root Exudates

Gas

PAH degrading

bacteria & fungi

water activity gradient

Leachate gradient

PAH/Oil Contaminated Soil

enzyme activity gradient

Temperature gradient

Eh gradient

Solubilization

PAH degrading

bacteria & fungi

Street

Gas Migration

Transport

Dolomite

Layer

Ditch

Methanotrophic bacteria

Leachate Collection

Gas Injection

clay

Leachate

Perched water table

Unsaturated

zone

Natural Attenuation

clay

Ground Water Table

Layers of reduced permeability

Saturated aquifer

groundwater flow

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COLUMN EXPERIMENT

COLUMN A - ACTIVELY AERATED + COMMERCIAL FERTILIZER

COLUMN B - ACTIVELY AERATED + NH4NO3 + TEP

COLUMN C - ACTIVELY AERATED + NH4NO3 + (NH4)3PO4

COLUMN D - PASSIVELY AERATED + COMMERCIAL FERTILIZER

expedited site characterization
Expedited Site Characterization
  • An expedited site characterization of the Czechowice Oil Refinery waste lagoon was performed by Ames Laboratories
  • Quantitative laboratory analyses as well as qualitative field techniques such as Cone Penetrometer based florescence probes, ground penetrating radar and horizontal well drilling was used to provide a physical and chemical characterization of the site.
  • BTEX, PAH and Metals were selected as target compounds based on the operating history of the refinery. IETU used the results to produce an environmental risk assessment.
  • The waste lagoons possess a natural clay bottom and no contaminates have been found directly beneath the lagoon. However, BTEX has been found at deeper depths which suggests a separate source.
risk assessment
Risk Assessment

Three Scenarios Postulated

I - Adult, On-site Future Construction/Remediation

Dermal, inhalation & ingestion during work at lagoons.

II - Adult, Industrial (I.e. Refinery Worker)

Dermal, inhalation & ingestion during associated work at lagoons.

III - Adult, On-site Groundwater, Future Irrigation

Dermal, inhalation & ingestion from groundwater during work or irrigation.

aeration leachate collection system
Sampling

Main

(solid)

Nutrients

Cell divider

Heinjection

Air injection

Active

section

Recirculation

pump

A

Sump

Lateral (perforated)

14 total

A

Passive section

Aeration/leachate collection system
sampling points
Sampling points

Active

section

Passive section

slide19
Detail A

Piezometer

(typical)

Biopile material

(1 - 1.5 M)

Cover

(20 - 30 cm)

Leachate dripping

Cell divider

Drainage/injection layer

(dolomite, 20 - 30 cm)

Leachate collection

Undisturbed earth

Moisture & Temperature

Baroball™

contaminants of concerns betx
Contaminants of concerns - BETX

Multi-use Indust. COF

Benzene 0.2 100 27.4

Ethylbenzene 1.0 200 3.3

Toluene 1.0 200 14.6

Xylenes 1.0 100 7.3

All values in mg/kg

Polish Maximum Contaminant Level (MCL) guidelines

(Industrial Use, 0-2 M) (Multiple Use, 0,3-15 M)

tph inventory
TPH Inventory

TPH concentration

  • Average 27.42 g/kg
  • Minimum <1 g/kg
  • Maximum 95 g/kg

Total TPH inventory158 metric tons

operating plan
Operating Plan
  • Initial systems tests (1 week).
  • Background testing (2-3 weeks).
  • Respiration test (1 week).
  • First Operating Campaign (3 months)
    • no nutrient amendments (dependent on initial tests)
    • air injection continuous, flow regulated by temperature 40-50°C
  • Subsequent Operating Campaigns (3 months each)
    • season differences
    • nutrient amendments
    • pulsed air injection
    • higher and lower flow rates for air injection
    • higher or lower leachate recirculation rates
four operating campaigns
Four Operating Campaigns

1. October 97 - January 98: start up and mild aeration

2. February 98 - April 98: intensive aeration

3. May 98 - June 98: aeration, nutrients

4. July 98 - September 98: aeration, nutrients, leachate recirculation

sample and analysis
Sample and Analysis
  • soil

microbiology, metals, BETX, TPH, PAH, nutrients, moisture, temperature, pH

  • soil gases

VOC, TPH, PAH, CO2, CH4, O2, pressure

  • leachate

microbiology, TPH, PAH, nutrients, conductivity, BOD, COD, pH

biodegradation rates mg kg day
Biodegradation Rates (mg/kg/day)

Campaign Average Passive Active

OC-1 80 44 119

OC-2 88 82 94

OC-3 < 33 33 0

before
Before

After82 metric tons

slide30
D Area Oil Seepage Basin

2 trenched horizontal wells at 3 m

1 blower (200 scfm)

Methane, N2O, TEP

In less than 6 months

Methylene Chloride: 2300 ppb to < 2 ppb

Vinyl Chloride: 300 ppb to < 5 ppb

Dichloroethylene: 100 ppb to < 2 ppb

Trichloroethylene: 100 ppb to < 5 ppb

Tetrachloroethylene: 50 ppb to <10 ppb

BTEX: 50 ppm to < 1 ppm

No Action ROD filed 6/98

slide31
Aerobic Landfill Bioreactor

CO2, O2, CH4

CO2, O2, CH4

Temporary Cover System

Leachate

Recirculation

Pump

Air

Blower(s)

Sanitary Waste

Sump

CompositeLiner

Aquifer

(American Technologies Inc., 1997)

typical vapor point
Typical Vapor Point

60

CH4 (%)

CO2 (%)

O2 (%)

50

Degrees C

40

30

20

10

0

1/10/97

1/30/97

2/19/97

3/11/97

3/31/97

4/20/97

5/10/97

5/30/97

6/19/97

7/9/97

7/29/97

8/18/97

(American Technologies Inc., 1997)

Date

landfill leachate parameters
Landfill Leachate Parameters

Parameter Before Injection After Injection

BOD (ppm) 1100 17-110

TOC (ppm) 1130 28

Iron (ppm) 110 0.3

Acetone (ppb) 1700 120

MEK (ppb) 690 80

Toluene (ppb) 1500 8

Methylene Chloride (ppb) 250 0

Fecal coliforms (CFU/100ml) 1,950,000 0

Temperature (°F) 60 120-160

Moisture Content (%) 80 95

Leachate Treatment (gal/monthly) 150,000 0

(American Technologies Inc., 1997)

aerobic landfill bioremediation
Aerobic Landfill Bioremediation
  • Demonstrated:
    • increased biodegradation rate
    • increased subsidence
    • eliminated need for leachate treatment
    • stabilized refuse mass sooner
    • decreased long-term liability and monitoring costs
    • decreased leaching of metals and organic contaminants
    • decreased methane generation
    • Reduced life cycle costs
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