RTDF TPH Subgroup Phytoremediation Field Trials: Results and Preliminary Conclusions. Acknowledgements. RTDF Cooperators under the leadership of

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1 RTDF TPH Subgroup Phytoremediation Field Trials: Results and Preliminary Conclusions Peter Kulakow and Xiujuan Feng Kansas State University Acknowledgements RTDF Cooperators under the leadership of Steve Rock Lucinda Jackson Phil Sayre USEPA Technology Innovation Office Environment Canada Great/Plains Rocky Mountain HSRC Midwest HSRC Henry Camp - ICF Consulting

2 RTDF Partners US Environmental Protection Agency Environment Canada Major Oil Corporations Petroleum Environmental Research Forum Public Utility Corporations US Department of Defense Universities Environmental Consultants Deep-Rooted Species 4 ACCORDING TO: Typical Lawn Grass Efficient Root Producer Feet Feet Kentucky Bluegrass Lead Plant Missouri Goldenrod Indian Grass Compass Plant Porcupine Grass Heath Prairie Big Blue Pale Prairie Aster Cordgrass Stem Purple Dropseed Coneflower Side Oats Grama False Boneset Switch Grass White Wild Indigo Little Blue Stem Rosin Weed Purple Prairie Clover June Grass Cylindric Blazing Star Buffalo Grass ft Root Systems of Prairie Plants - From the U.S. EPA Handbook on Natural Landscapes

3 Goal Assess the efficacy of vegetation to enhance degradation of aged petroleum hydrocarbons in soil Is there evidence that vegetation enhances progress toward practical environmental management objectives for petroleum sites within 3 years? Rationale for Approach Hydrocarbon degradation Changes are slow and subtle Monitoring is needed for a long period Contaminant distribution in soil is variable Standard protocol facilitates comparisons among locations allowing for site specific adjustments

4 Experimental Design Standardized Protocol Randomized complete block design with four replications Treatments with site specific adjustments Standardized grass/legume mixture Local-optimized treatment Unvegetated/unfertilized Control Minimum plot size: 2 x 2 ft. ROADWAY BERM Site I PONDED AREA 225 ft A = Do Nothing B = Fertilizer Only C = RTDF Mix D = Prairie Mix 14 ft REVISED LAYOUT A D B C 1 ft HEAVIER FORESTED AREA 125 ft ROADWAY BERM Hydrant X Gravelly Area D C A B B A C D 11 ft 7 ft STAGING AREA FOR FIELD ACTIVITIES A D C B 35 ft 1 ft 2 ft Access Ramp 185 ft ROADWAY BERM Surface Pipe RTDF: 4 lbs fescue / 1 lbs p.rye / 5 lbs clover Surface Prairie: 1 lbs prairie / 25 lbs fescue Pipe

5 Soil Composite 8 soil cores/plot Two depths: 15 cm and cm Sample Annually for 3 growing seasons Vegetation Sampling Plan Above ground biomass production Plant species composition Root growth Hydrocarbon uptake at final sampling Site A May 21 Hydrocarbon Uptake Sampling

6 Sample Preparation and Analysis Flow 1 grams of sample is Soxhlet extracted Weight measured gravimetrically Extract column cleanup Weight measured gravimetrically Split for instrument analyses TPH (GC/FID) OIL & GREASE (GRAV) TPH (GRAV) PAH (GC/MS) HOPANE (GC/MS) Example GC/FID Chromatogram Output Resolved Components (TPH RES) Unresolved Components (TPH) Response_ D\FID2B Time

7 Example Expanded PAH Output PAH Homologous Series Sulfur-containing Heterocyclics 5- and 6-Ring PAH 3 Analyte Profile Histogram "2A4455: G11T1A SOIL" 25 Concentration ug/kg Naphthalene C1-Naphthalenes C2-Naphthalenes C3-Naphthalenes C4-Naphthalenes Acenaphthylene Acenaphthene Biphenyl Fluorene C1-Fluorenes C2-Fluorenes C3-Fluorenes Anthracene Phenanthrene C1-Phenanthrenes/anthracenes C2-Phenanthrenes/anthracenes C3-Phenanthrenes/anthracenes C4-Phenanthrenes/anthracenes Dibenzothiophene C1-Dibenzothiophenes C2-Dibenzothiophenes C3-Dibenzothiophenes Fluoranthene Pyrene C1-Fluoranthenes/pyrenes C2-Fluoranthenes/pyrenes C3-Fluoranthenes/pyrenes Benzo[a]anthracene Chrysene C1-Chrysenes C2-Chrysenes C3-Chrysenes C4-Chrysenes Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[e]pyrene Benzo[a]pyrene Perylene Indeno[1,2,3,-c,d]pyrene Dibenzo[a,h]anthracene Benzo[g,h,i]perylene Compounds TPHCWG Sample Preparation and Analysis Flow 1 grams of sample is vortex extracted in pentane Extract is fractionated and cleaned Each fraction submitted for instrument analyses TPH Ranges (9) TPH Ranges (9)

8 Response_ Time Response_ Time Response_ Time D\FID2B D\FID2B D\FID1A Example TPHCWG Chromatogram Output Quantitation divided in ranges related to boiling point Response_ D\FID1A Time TPHCWG Data TPH-CWGM TPH-CWGM Total Total Resolved 21 Resolved 21 Total Total PHC 2 PHC 2 Total Total Resolved 18 Resolved 18 TPH 15 TPH 15 TPH>nC6-nC8 ND TPH>nC6-nC8 ND TPH>nC8-nC1 1.3 TPH>nC8-nC1 1.3 J J TPH>nC1-nC12 1 TPH>nC1-nC12 1 J J TPH>nC12-nC16 12 TPH>nC12-nC16 12 TPH>nC16-nC21 21 TPH>nC16-nC21 21 TPH>nC21-nC25 24 TPH>nC21-nC25 24 TPH>nC25-nC3 5 TPH>nC25-nC3 5 TPH>nC3-nC35 28 TPH>nC3-nC35 28 TPH>nC TPH>nC Total Total Resolved 33 Resolved 33 TPH 48 TPH 48 TPH>nC6-nC7 TPH>nC6-nC7 (B) ND (B) ND TPH>nC7-nC8 TPH>nC7-nC8 (T) ND (T) ND TPH>nC8-nC1 ND TPH>nC8-nC1 ND TPH>nC1-nC12.15 TPH>nC1-nC12.15 J J TPH>nC12-nC16 26 TPH>nC12-nC16 26 TPH>nC16-nC21 9 TPH>nC16-nC21 9 TPH>nC21-nC25 74 TPH>nC21-nC25 74 TPH>nC25-nC3 12 TPH>nC25-nC3 12 TPH>nC3-nC35 98 TPH>nC3-nC35 98 TPH>nC35+ 7 TPH>nC35+ 7

9 Thirteen RTDF Field Site Locations April 1999 Site A Refinery Site Three Complete Growing Seasons June 2 May 21

10 Site B - Closed Refinery RTDF Mix Unvegetated Poplar/Willow Hackberry 4 Site B, OH ( ) 3 Temperature ( o C) Precipitation (cm) /1/98 4/1/98 7/1/98 1/1/98 1/1/99 4/1/99 Planting 7/1/99 1/1/99 1/1/ 4/1/ 7/1/ 1/1/ Time (month) 1/1/1 4/1/1 7/1/1 1/1/1 1/1/2 4/1/2 7/1/2 1/1/2 1/1/3-1 -5

11 Three Alaskan Sites Cold Regions Site C Site E Site D Site C ( ) Temperature ( o C) T Max T Min Pcp Precipitation (cm) /1/98 4/1/98 7/1/98 1/1/98 1/1/99 4/1/99 Planting 7/1/99 1/1/99 1/1/ 4/1/ 7/1/ 1/1/ Time (month) 1/1/1 4/1/1 7/1/1 1/1/1 1/1/2 4/1/2 7/1/2 1/1/2 1/1/

12 Temperature ( o C) /1/98 4/1/98 7/1/98 1/1/98 1/1/99 4/1/99 7/1/99 Planting T Max T Min Pcp Site E ( ) 1/1/99 1/1/ 4/1/ 7/1/ 1/1/ Time (month) 1/1/1 4/1/1 7/1/1 1/1/1 1/1/2 4/1/2 7/1/2 1/1/2 1/1/ Precipitation (cm) Site F Manufactured Gas Plant Willow/Poplar Mix RTDF Mix

13 Site F New York North Willow Grass Willow Volunteer Rep. 1 Rep. 2 Volunteer No Vegetation No Vegetation Grass No Vegetation Willow Grass No Vegetation Gate Rep. 4 Rep. 3 Gravel road Grass Volunteer Willow Volunteer Water tank Site G Kansas Motor Pool Waste Lagoon Sediments

14 Site G ( ) 4 25 Temperature ( o C) T Max T Min Pcp Precipitation (cm) /1/98 4/1/98 7/1/98 1/1/98 1/1/99 4/1/99 Planting 7/1/99 1/1/99 1/1/ 4/1/ 7/1/ Time (month) 1/1/ 1/1/1 4/1/1 7/1/1 1/1/1 1/1/2 4/1/2 7/1/2 1/1/2 1/1/3-5 Site I Closed Refinery Illinois October 21 May 22

15 Site H Closed Distribution Facility Rhode Island October 22 Site J Production Site Arkansas

16 Site K Manufactured Gas Plant, Indiana Site L SK, Canada Buried Flare Pit Planted June 22

17 Results Status of Field Sites 36 Data Sets Planting Sampling Events Date Time Year 1 Year 2 Year 3 Year 4 Site A, CA Site B, OH Site C, AK Dec-98 Apr-99 Jun-99 Nov-2 Site D, AK Site E, AK Aug-98 Aug-98 Aug-98 Site F, NY Jun-99 Oct-2 Site G, KS Oct-99 Oct-2 Site H, RI May-1 May-1 Oct-2 Nov-3 Site I, MO Nov- Oct-2 Nov-3 Site J, AR Oct-99 Oct-1 May-2 Site K, IN May-99 Site L, SK Canada Jun-2 Jun-2 Oct-2 Oct-4 Site M, AL Canada May-3 May-3 Oct-5

18 Dealing with the Data Nondetect data Used a nonzero substitution Numerous derived variables such as Total PAHs >1 variables analyzed Analyzed Original data Hopane normalized data Statistical Analysis Randomized Complete Block Design Soil depth usually analyzed separately Time is a repeated measure Derived variables approach Each time interval analyzed separately Considered assumptions of analysis of variance Homogeneity of variances most important Treatment differences tested by analysis of variance and lsd tests.

19 x2 45 Total PAHs mg/kg Site A 95% Confidence Ellipses for RTDF Data x2 45 Total PAHs mg/kg Standard Reference Sample Site A TPH (mg/kg) High Variability in TPH and PAH Concentrations Between locations Original composition of contaminants Previous degradation Climate Within locations Spatial variation some accounting for in blocking of experiments Time, Depth, and Treatment effects Management Decisions Within samples Sample heterogeneity Analytical Variation Instrumentation Laboratory Procedures

20 95% Confidence Ellipses for RTDF Data Total PAHs mg/kg x Site A Total PAHs mg/kg x Site F Total PAHs mg/kg TPH (mg/kg) x2 x Site B 3 Site G Total PAHs mg/kg TPH (mg/kg) TPH (mg/kg) TPH (mg/kg) 95% Confidence Ellipses for RTDF Data x2 45 x2 45 Total PAHs mg/kg Site C Total PAHs mg/kg Site D x2 45 TPH (mg/kg) TPH (mg/kg) Total PAHs mg/kg Site E TPH (mg/kg)

21 95% Confidence Ellipses for RTDF Data x2 45 x2 45 Total PAHs mg/kg Site H Total PAHs mg/kg Site J TPH (mg/kg) TPH (mg/kg) x2 45 x2 45 Total PAHs mg/kg Site I Total PAHs mg/kg Standard Reference Sample TPH (mg/kg) TPH (mg/kg) Site F Treatment Means for Total PAHs for to 15 cm Depth Concentration (mg/kg) Months Volunteer RTDF Mixture Unvegetated Willow/Poplar

22 Site F PAH Treatment Means 18 Months, Depth to 15 cm 25 2 Concentration (mg/kg) CN C1N C2N C3N C4N ACEY ACE BIP CF C1F C2F C3F CA CP C1P_A C2P_A C3P_A C4P_A CD C1D C2D C3D PAH FLANT PYR C1F_P C2F_P C3F_P BAA CC C1C C2C C3C C4C BBF BKF BEP BAP PER INDENO DAH BGP Volunteer Standard Unvegetated Willow Treatment Differences for 41 PAHs >25% of PAHs different by ANOVA (P<.5) Depth Site A Site B Site C Site D Site E Site F Site G Site H Site I Site J Site K Site L Site M A Time B Sampling Events Year 1 Year 2 Year 3 A B A B A B

23 Treatment Differences for 41 Normalized PAHs >25% of PAHs different by ANOVA (P<.5) Depth Site A Site B Site C Site D Site E Site F Site G Site H Site I Site J Site K Site L Site M A Time B Sampling Events Year 1 Year 2 Year 3 A B A B A B Site G Hopane Normalized Total PAHs 15 cm Depth PAH to Hopane Ratio T1-T T2-T Months Native Standard Unvegetated

24 Depth Site A Site B Site C Site D Site E Site F Site G Site H Site I Site J Site K Site L Site M Treatment Differences Change in 41 Normalized PAHs >25% of PAHs different by ANOVA (P<.5) Time 1-Time A.44 B Time 2-Time A B Interval Time 3-Time A.37 B.42 Time 3-Time A B 8 Site G Hopane Normalized Total PAHs cm Depth 7 PAH to Hopane Ratio Months Native Standard Unvegetated

25 Total Petroleum Hydrocarbons -- Plot G11, -15 cm Depth -months TPH 13, mg/kg 12-months 9,5 mg/kg 24-months 3,9 mg/kg Site G to 15 cm Depth 22% Time 78% RTDF Mix Vegetation 24 months No Vegetation 24 months 3% 23% 7% 77%

26 Site G to 15 cm Depth Fractions Time 9% 62% 11% 14% C6-8 C8-1 C1-12 C12-16 C16-21 C21-35 C35+ RTDF Mix Vegetation 24 months 3% 1% 12% 8% No Vegetation 24 months 7% 13% 74% 7% 7% 77% Site G to 15 cm Depth Fractions Time 46% 5% 2% 24% C8-1 C1--12 C12-16 C16-21 C21-35 C35+ RTDF Mix 24 months 17% 14% 15% 7% 17% No Vegetation 24 months 69% 7% 6% 77%

27 RTDF Trial Site A -- Hopane Normalized Total PAHs 15 to 45 cm 25 PAH to Hopane Ratio Months Native Standard Unvegetated RTDF Trial Site A -- Hopane Normalized Total PAHs to 15 cm 14 PAH to Hopane Ratio Months Native Standard Unvegetated

28 RTDF Trial Site J -- Total Petroleum Hydrocarbons to 15 cm Concentration (mg/kg) Months Bermudagrass Standard Unvegetated Status of Project 75% data available 4 new datasets within next month 7 of 13 locations are finished 5 have data for 3 growing seasons Site F will continue for 3 more years less than 3 growing seasons for 2 sites Additional results expected for 7 locations 2 new locations in Canada More data analysis

29 Primary Results to Date Sites G J A,D,F A Evidence strong evidence of positive vegetation effect - Highly degradable source, lower variation strong evidence of positive vegetation effect only with an alternative sampling method evidence of emerging vegetation effect - Needs confirmation over longer period evidence of negative vegetation effect in surface soil only Preliminary Conclusions Is there evidence that vegetation enhances progress toward practical environmental management objectives for petroleum sites within 3 years? Yes, at some locations. Use site specific

30 Preliminary Conclusions Best locations -- Highly degradable source material with low to moderate hydrocarbon concentrations near riskbased levels. Site characterization important Net environmental benefits and cost may support use of phytotechnologies. Preliminary Conclusions Highly weathered sites Evidence of vegetation effect difficult to demonstrate. High variability from multiple sources obscures potential treatment effects. Initial composition and aging limits potential for further degradation. Effects are long term and three years not always sufficient. Vegetation has both positive and negative effects on bioavailability.

31 Preliminary Conclusions Highly weathered sites Phytotechnologies may be part of a long term ecological restoration strategy. Phytorestoration that includes continued slow remediation and stabilization processes. Need to understand bioavailability and risk. The Future Improvements to the protocol Additional results and analyses Final report Results on RTDF website

32 TPH In Soil Subgroup