PAHPAH PhytodegradationPhytodegradation && HabitatHabitat RestorationRestoration atat aa HistoricHistoric IndustrialIndustrial CokeCoke OvenOven FacilityFacility
Clayton Rugh Michigan State University
Endang Susilawati Donald K. Russell Michigan State University Ford Motor Company
Laura Carreira John C. Thomas Applied Phytogenetics Univ of Michigan-Dearborn RougeRouge ManufacturingManufacturing ComplexComplex (Dearborn, MI) Rouge Heritage Project – conceptualized by McDonough +Partners RougeRouge ManufacturingManufacturing ComplexComplex –– CokeCoke OvenOven AreaArea
Soil collection locations from the Coke Oven Facility PolyaromaticPolyaromatic HydrocarbonHydrocarbon (PAH)(PAH) ChemicalChemical StructuresStructures EcologicalEcological oror IntrinsicIntrinsic PhytoremediationPhytoremediation
UseUse ofof managed,managed, naturalnatural systemssystems
EmphasisEmphasis onon sustainabilitysustainability
RegionalRegional nativenative speciesspecies ++ compostscomposts
PlantPlant--EnhancedEnhanced PAHPAH BiodegradationBiodegradation
RhizostimulationRhizostimulation ofof bacterialbacterial dioxygenasedioxygenase activityactivity
RootRoot exudatesexudates asas nutrientsnutrients andand coco--metabolitesmetabolites PhytoPhyto FieldField TrialTrial -- SelectedSelected UplandUpland PlantPlant SpeciesSpecies Scientific Name Common Name Andropogon gerardii Big Bluestem Andropogon scoparius Little Bluestem Grasses Hystrix patula Bottlebrush Grass Spartina pectinata Prairie Cordgrass Carex sprengelii Sprengel Sedge Sedges Scirpus atrovirens Bulrush Amorpha canescens Leadplant Aster novae-angliae New England Aster Cirsium discolor Pasture Thistle Eupatorium perfoliatum Boneset Herbaceous Eupatorium purpureum Joe-Pye Weed Geum triflorum Prairie Smoke Lobelia cardinalis Cardinal Flower Silphium teribinthinaceum Prairie-dock Ceanothus americanus New Jersey Tea Physocarpus opulifolius Common Ninebark Shrubs Spirea alba Meadowsweet Viburnum dentatum Arrowhead Viburnum Phytoremediation Demonstration Plots Constructed at Allen Park Clay Mine Landfill by URS Corp.
Phyto Treatment Facility Layout
Control Upland Wetland Water Plot Plot Plot Mgmt System
Cross-section detail of treatment plots
Geotech PAH contaminated soil 24” liner
4” grade 20 feet Gravel HDPE FordFord PhytoremediationPhytoremediation FieldField TrialTrial PlotsPlots
Upland Site
Wetland Site
September 2001
September 2002 UplandUpland PlotPlot SoilSoil [tPAH][tPAH] -- SeptSept 20012001 (Yr(Yr 1)1)
140 120 Starting Soil tPAH ~ 130 ppm
) 100 m p p
( 80 AH] P t 60 [ l i o
S 40 20
0 i a m s a e i ii is b s s s la ius t a m d lor el m l ed l iu eu r cen li tu ar o g a a nu l en tu um um r s ina g a r n eu in ant a ir tat or opa e n li e sc e c d l S. ic ifo pa n fl rpu ect -a g di r na p r ul rov . ri sc an p e rfo H t pu a e A. C. . sp hi . car Un me at . de . A. . c S. v nt L a . op V G E. A o p C . P S. n E. ibi C er A. t S. UplandUpland PlotPlot SoilSoil [tPAH][tPAH] -- SeptSept 20012001 (Yr(Yr 1)1)
140
120 < Unplanted
) 100 α = 0.1 m p p
( 80 AH] P t 60 [ l i o
S 40 20
0 i a m s a e i ii is b s s s la ius t a m d lor el m l ed l iu eu r cen li tu ar o g a a nu l en tu um um r s ina g a r n eu in ant a ir tat or opa e n li e sc e c d l S. ic ifo pa n fl rpu ect -a g di r na p r ul rov . ri sc an p e rfo H t pu a e A. C. . sp hi . car Un me at . de . A. . c S. v nt L a . op V G E. A o p C . P S. n E. ibi C er A. t S. FinalFinal SoilSoil tPAHtPAH ConcentrationConcentration forfor SelectedSelected TreatmentsTreatments
160 SCIATR
140 PHYOPU
120 ASTNOV
UNPLNT 100 EUPPUR
80 LOBCAR
60 ANDGER
SPAPEC 40 Soil tPAH (in ppm) Soil tPAH (in Soil tPAH (in ppm) Soil tPAH (in 20
0 0 1 2 3 YearsYears afterafter plantingplanting ProjectedProjected SoilSoil tPAHtPAH ConcentrationConcentration forfor PhytoPhyto TreatmentsTreatments
160
140
120
100
80
60 Soil tPAH (in ppm) Soil tPAH (in Soil tPAH (in ppm) Soil tPAH (in 40
20 ~65% Reduction = Phytoremediation Limit?
0 0 1 2 3 4 5 YearsYears afterafter plantingplanting Solubility Properties of Selected POPs
PCBs log(Kow) PAHs log(Kow)
Biphenyl 4.1 Benzene (C6H6) 2.1
2-CBP (1 Cl) 4.5 Naphthalene (C10H8) 3.4
4-CBP (1 Cl) 4.4 Phenanthrene (C14H10) 4.5
4,4'-CBP (2 Cl) 5.2 Anthracene (C14H10) 4.5
2,4,5-CBP (3 Cl) 5.7 Chrysene (C18H22) 5.6
2,3,'4,4'-CBP (4 Cl) 6.3 Benzo(a)pyrene (C20H12) 6.5
Decachloro-BP (10 Cl) 8.2 Benzo (g,h,i)perylene (C 22H12) 7.2
Hydrophobicity is measured as solubility in Octanol divided by Aqueous Solubility
Ex. Phenanthrene has a log Kow = 4.46
…which equals 28840.32X more Phen in octanol phase than in aqueous Particle-Scale Understanding of the Bioavailability of PAHs in Sediment. Talley, Ghosh, Tucker, Furey, Luthy. 2002. ES&T 36:477-483 ParticleParticle FractionationFractionation ofof RougeRouge SoilSoil (Luthy lab, Stanford Univ.) Size Separation @ 250µ & Density Separation @ 1.8 g/ml (sat’d CsCl)
Soil Organic Fraction 21% w/w
Light Soil (63-250 µ) Light Soil (250-1000 µ) Soil Mineral Fraction 79% w/w
Heavy Soil (63-250 µ) Heavy Soil (250-1000 µ) ParticleParticle FractionationFractionation ofof RougeRouge SoilSoil (Luthy lab, Stanford Univ.) Size Separation @ 250µ & Density Separation @ 1.8 g/ml (sat’d CsCl)
Soil Organic Fraction 21% w/w 75% tPAH content
Light Soil (63-250 µ) Light Soil (250-1000 µ) Soil Mineral Fraction 79% w/w 25% tPAH content
Heavy Soil (63-250 µ) Heavy Soil (250-1000 µ) ProgressiveProgressive MechanismMechanism ofof SoilSoil PhytoPhyto TreatmentsTreatments
160
140 Rhizodegradation 120
100 Phytopolishing 80 Geostabilization 60 Soil tPAH (in ppm) Soil tPAH (in Soil tPAH (in ppm) Soil tPAH (in 40
20
0 0 1 2 3 4 5 YearsYears afterafter plantingplanting PartPart II.II. RhizosphereRhizosphere EcologyEcology InfluencesInfluences •• RootRoot QuantificationQuantification andand DensityDensity
ExcavationExcavation andand isolationisolation ofof rootroot biomassbiomass
WhatWhat isis aa “rhizosphere”?“rhizosphere”?
•• “The“The areaarea ofof thethe soilsoil influencedinfluenced byby rootroot systems…”systems…”
-- estimatedestimated toto bebe asas muchmuch asas 3%3% ofof soilsoil volumevolume (J. Fletcher, Univ. of Oklahoma)
-- soilsoil thatthat “stays“stays attachedattached toto rootsroots afterafter shaking”shaking” RootRoot BiomassBiomass DensityDensity relativerelative toto SoilSoil (cu.(cu. yd.)yd.)
120
100
80
60
40
20 Root Density in PPT (wt / wt) Root Density in Root Density in PPT (wt / wt) Root Density in 0
S T N R O V R E I R R RI T R U R R C B N O T A A P E L E N A C P M D E P AT T E A C GE S N A R PU U C O I L P PL D T RS PP P S B C PI BD A CI S SI S MO N ND U GE HY HY PA VI UN A A A AS CA CE EU E LO P S treatmenttreatment RootRoot BiomassBiomass DensityDensity relativerelative toto SoilSoil (cu.(cu. yd.)yd.)
40
35
30
25
20
15
10
5 Root Density in PPT (wt / wt) Root Density in Root Density in PPT (wt / wt) Root Density in 0 XX
S R T N R O V R I R R RI T R U R C B N O E T A A T E L E N A E C P M E U P A T E L G S N RD P U C O IA D T A I IL B OC RS A C P PP Y CI S AP NP M ND ND GE YSPOB S SP VI U A A A AS CA CE EU EU H L PH SP treatmenttreatment RootRoot BiomassBiomass InfluenceInfluence onon PAHPAH ReductionReduction
50
45
40 35
30
25
20
15 10 Soil tPAH Reduction (%) Soil tPAH Reduction Soil tPAH Reduction (%) Soil tPAH Reduction 5
0 020406080100
RootRoot DensityDensity ((pptppt Soil)Soil) RootRoot BiomassBiomass InfluenceInfluence onon PAHPAH ReductionReduction
50
45
40 35
30
25
20
15 10 Soil tPAH Reduction (%) Soil tPAH Reduction Soil tPAH Reduction (%) Soil tPAH Reduction 5
0 020406080100 RootRoot DensityDensity ((pptppt Soil)Soil) RootRoot--MicrobeMicrobe EcologyEcology InteractionsInteractions
•• BacterialBacterial RhizostimulationRhizostimulation
RootRoot--enhancedenhanced bacteriabacteria cellcell densitydensity
EnrichmentEnrichment ofof PAHPAH biodegradersbiodegraders viavia cometabolismcometabolism
•• BacterialBacterial MetabolicMetabolic EnrichmentEnrichment
ExpansionExpansion ofof bacterialbacterial metabolicmetabolic capabilitiescapabilities PAHPAH MetabolismMetabolism SpraySpray PlatePlate AssayAssay
SpecificSpecific PAHPAH biodegraderbiodegrader assayassay
SoilSoil extractsextracts platedplated forfor CFUsCFUs
PhenanthrenePhenanthrene residueresidue appliedapplied
ClearClear zoneszones == biodegradersbiodegraders == ZFUsZFUs BacterialBacterial PhenanthrenePhenanthrene--DegradingDegrading IsolatesIsolates Spray-Tested against Multiple PAHs
Phenanthrene Anthracene
Fluoranthene Pyrene BacterialBacterial PhenanthrenePhenanthrene--DegradingDegrading IsolatesIsolates Spray-Tested against Multiple PAHs k-region Phenanthrene Anthracene
Bay-region
Fluoranthene Pyrene Bacterial Isolates Tested against Multiple PAHs Over 2100 Phenanthrene Degraders Isolated ~110 isolates from each Phyto treatment including untreated soils PhenD isolates Spray-Tested against other PAH compounds
x x x
Phenanthrene
Anthracene Pyrene Phenanthrene Degraders tested on other PAHs
45 AnthD FlraD PyreD 40 *
35 * * * 30 * * * Isolates 25 *
D * 20
15
% of Phen 10
5
0
AMO AND AND AST CAR CEA CIR EUP EUP GEU HYS LOB PHY SCI SIL SPA SPI VIB UNP UNT CAN GER SCO NOV SPR AME DIS PER PUR TRI PAT CAR OPU ATR TER PEC ALB CEN LNT ROU Soil Treatment α = 0.10 Soil Treatment * (plant spp abbr) PartPart III.III. CommunityCommunity EcologyEcology InfluencesInfluences
•• VegetatedVegetated CommunityCommunity PersistencePersistence
FieldField installationinstallation strategystrategy
SusceptibilitySusceptibility toto herbivorherbivores,es, disease,disease, encroachmentencroachment
•• VegetatedVegetated CommunityCommunity ExpansionExpansion
SSelfelf--propagationpropagation andand competitivenesscompetitiveness PersistencePersistence ofof PlantedPlanted PhytoPhyto SpeciesSpecies (3(3rd Yr)Yr)
120
100
80
60
40
20 % Species Persistence
% Species Persistence 0
E I T B N R O V R IS R R R U R R C N A R T E E C P D E U P E AL G NO S AM R UT CA IA T PE I D OC D DS T R A PP PP E B YO IL A IB CI YSPA S SP G H SC V AM AN AN AS CA CE EU EU LO PH SP
Plant Species (abbreviation) PhytoPhyto SpeciesSpecies ExpansionExpansion withinwithin PlotPlot (3(3rd Yr)Yr)
35
30
25 Coverage Coverage 20
15 Spp Spp
10
5 % New % New 0
E I T N R O V R IS R R R U R R C B N A E O M R A T E L C P E T P A E C G S N S A RD P PU U C OP IA T IA DE O D D T R A P S B Y IL AP B CI UP GE SC S SP VI AM AN AN AS CA CE EU E HY LO PH SP
Plant Species (abbreviation) RelativeRelative DensityDensity MapMap ofof PhytoPhyto CommunityCommunity SpeciesSpecies
Selected Phyto Species should be perennial, competitive and prolific ResultsResults SummarySummary
PlantedPlanted treatmentstreatments werewere typicallytypically moremore effectiveeffective atat reducingreducing soilsoil PAHsPAHs thanthan unplantedunplanted treatmentstreatments
DifferentDifferent plantplant speciesspecies hadhad differentdifferent effectseffects onon bacterialbacterial biodegraderbiodegrader communitycommunity
PlantsPlants generallygenerally enrichedenriched broadbroad--rangerange bacterialbacterial PAHPAH metabolicmetabolic capabilitiescapabilities
VariedVaried plantplant communitycommunity dynamicsdynamics amongamong speciesspecies –– somesome moremore suitablesuitable forfor stablestable habitathabitat restorationrestoration RougeRouge ManufacturingManufacturing ComplexComplex PhytoremediationPhytoremediation TrialsTrials Dearborn, MI – May 2003
PlantedPlanted FallFall 0202 withwith ~24,000~24,000 IndividualIndividual PlantsPlants 34 ft 12 ft 34 ft Spp Spp A + C Sp B C + D + 36 ft Spp Sp D Sp A A + B C + D Spp ~12 ft 12 Spp B + D Sp C A + B 80 ft lant Community Subplots P combinations combinations spp spp = Tall Grasses or Trees = Low Shrubs = Large Shrubs = Tall Grasses or Trees = Low Shrubs = Large Shrubs = Short Grasses = Short Grasses 108 plant 108 plant Sp D Sp C Sp B Sp A Sp D Sp C Sp B Sp A Rouge Phyto Exhibit – 12 Plots X 9 Subplots = 12 Plots X 9 Subplots = RougeRouge PhytoPhyto ExhibitExhibit –– JuneJune 20042004 -- AerialAerial OverviewOverview RougeRouge ComplexComplex PhytoremediationPhytoremediation InstallationInstallation ExhibitExhibit JulyJuly 20042004 –– 22nd SeasonSeason Wildlife Recovery at the Industrial Brownfield Protected Species and Pollinators Hummingbird Moth
Blue-Flag Iris Wildlife Recovery at the Industrial Brownfield Protected Species and Pollinators Hummingbird Moth
Habitat and Beneficial Species Blue-Flag Iris
New England Aster
Praying Mantis Wildlife Recovery at the Industrial Brownfield Protected Species and Pollinators Hummingbird Moth
Habitat and Urban Beneficial Mammal Species Blue-Flag Iris Migration
New England Aster Big Bluestem
Praying Mantis Junkyard Dog Canus detroitii Recommended Phyto Species: Phyto and Weed-resistance rating: * = ok, ** = good, *** = excellent Habitat: U = upland, W = wetland (low-land), Type: G = grass, H = herbaceous Species Common Name Phyto Weed-R Habitat Type Andropogon gerardii Big Bluestem *** * U G Aster novae-anglicae New England Aster *** *** U or W H Carex sprengelii Sprengel Sedge ** *** U or W G Eupatorium perfoliatum Boneset ** *** U or W H Eupatorium purpureum Joe-pye Weed *** * U H Hystrix patula Bottlebrush Grass ** *** U G Panicum virgatum Switchgrass *** *** U G Physocarpus opulifolius Ninebark ** *** U H Scirpus atrovirens Green Bulrush *** *** U or W G Solidago patula Swamp Goldenrod ** *** U or W H Spartina pectinata Prairie Cordgrass ** *** U or W G Spirea alba Meadowsweet *** *** U H Viburnum dentatum Arrowwood Viburnum ** *** U H Potential PARAPHYTOREMEDIATION Species: Phyto and Weed-resistance rating: * = ok, ** = good, *** = excellent Habitat: U = upland, W = wetland (low-land), Type: G = grass, H = herbaceous Species Common Name Andropogon gerardii Big Bluestem BIOMASS RECOVERY Aster novae-anglicae New England Aster Carex sprengelii Sprengel Sedge Biocomposite Plastics – replacement for Eupatorium perfoliatum Boneset fossil fuel-derived products Eupatorium purpureum Joe-pye Weed Hystrix patula Bottlebrush Grass Bioenergy Crops – pelletized high-energy Panicum virgatum Switchgrass Physocarpus opulifolius Ninebark Cellulose Feedstocks – ethanol, etc. Scirpus atrovirens Green Bulrush Solidago patula Swamp Goldenrod Collaboration with: Spartina pectinata Prairie Cordgrass Ford Research LabsLabs Spirea alba Meadowsweet MSU Composite MaterMaterialials Center Viburnum dentatum Arrowwood Viburnum PotentialPotential SiteSite RedevelopmentRedevelopment // RehabilitationRehabilitation PlanPlan
Tree Row – Wind Break Phyto & Biomass Phyto Meadow Studies Tree Row – Wind Break
30 Acre Remediation / Rehabilitation Challenge Sustainable plant community for site stabilization and intrinsic bioremediation ~$8,000 - $20,000 per acre not including labor costs Optional industrial, site restoration, and educational opportunities Acknowledgements Funding Sources Ford Motor Company Environmental Quality Office Ford Land Development Corporation US Environmental Protection Agency – STAR Program Midwest Hazardous Substances Research Program, Region 5 US Department of Agriculture National Needs Fellowship Michigan Agriculture Experiment Station
Collaborators MSU Phytoremediation Lab Ford Research Labs UMD Plant Physiology Lab New Mexico State University