ENHANCED HYDROCARBON BIOREMEDIATION THROUGH THE ADDITION OF HUMIC SUBSTANCES PART II:

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ENHANCED HYDROCARBON BIOREMEDIATION THROUGH THE ADDITION OF HUMIC SUBSTANCES PART II: IMPROVED LAND TREATMENT AND STATIC-PILE COMPOSTING L. E. Liem and R. M. Facey (Hood Environmental, Sherwood Park) M. Fischer (Luscar Specialty Products, Edmonton)

RATIONALE Potential hydrocarbon contamination in soil Humic substances improve soil quality enhancing hydrocarbon biodegradation Excellent potential market over landfilling

SCOPE OF WORK Improved performance of humic substances in enhancing hydrocarbon biodegradation bulking agents and soil additives addition Laboratory experiments of land treatment and static-pile composting

GUIDELINES Canadian Council of Ministries of the Environment (CCME) Tier I for Petroleum Hydrocarbons (PHC) Agricultural application for fine grain soil

TREATMENT ALTERNATIVES Land treatment: lower capital & operation, less optimized process Static-pile composting: higher capital & operation, more optimized process

LAND TREATMENT 300 mm depth Manual tilling Mesophilic C:N = 20 to 25:1 50 to 75% field capacity

STATIC-PILE COMPOSTING 2 to 3 m depth Forced aeration Thermophilic C:N = 20 to 25:1 50 to 75% field capacity

SOIL PROPERTIES Parameter Moisture Field Capacity Porosity Bulk Density Clay Silt Sand Total Carbon Total Nutrient ph HPC Unit % % % kg/m 3 % % % % % - #/g Value 23 85 50 1,000 63 22 15 2.4 0.34 7.3 1,100

HYDROCARBON CONTAMINANT Diesel: 97% C 7 to C 22 @ 36.1 to 503.0ºC Evaporation < 0.1% @ 36 to 69 ºC

HYDROCARBON BIODEGRADATION Improve soil quality Increase hydrocarbon solubility in soil Enhance growth of soil microorganisms

HUMIC SUBSTANCES Provide available carbon to soil Maintain soil ph around neutral Increase solubility of hydrocarbons in soil Improve water retention in soil Dissolve clay aggregate Retain micronutrients in soil

HUMIC SUBSTANCES (Cont d) Parameter Organics ph Bulk Density Particle Size 75 to 180 < 75 Unit % - kg/m 3 micron micron Value 55 7.0 to 7.4 866 to 965 17% 83%

BULKING AGENTS Improve soil porosity Provide available nutrients Increase initial number of microorganisms Provide medium for microorganisms growth

BULKING AGENTS (Cont d) Parameter Unit Compost Wood-Mulch Moisture % 29 62 Field Capacity % Porosity % 50 50 Bulk Density kg/m 3 585 250 Particle Size % 18 (> 4 mm) 39 (> 4 mm) % 57 (0.5 to 4 mm) 53 (0.5 to 4 mm) % 25 (< 0.5 mm) 8 (< 0.5 mm) Total Carbon % 18.2 38.7 Total Nitrogen % 0.94 0.88 ph - 7.2 7.1 HPC #/g 250E6 77E6

SOIL ADDITIVES Improve hydrocarbon degradation Enhance microorganisms growth

SOIL ADDITIVES (Cont d) Component Extra-cellular enzymes Biostimulants: Bacterial culture Nutrients % (by weight) 10 60 30

EXPERIMENTAL DESIGN: Land Treatment Diesel: 0.25 to 0.5 % by weight Humic substances: 0 and 5% by weight Bulking agents: 0 and 50% by weight Soil additives: 0 and 0.1% by weight Temperature: ambient @ 20 C Aeration: tilling Moisture: 50% by weight

EXPERIMENTAL DESIGN: Static-Pile Composting Diesel: 0.25 to 0.5 % by weight Humic substances: 0 and 5% by weight Bulking agents: 0 and 50% by weight Temperature: heated to 50 C Aeration: forced Moisture: 50% by weight weekly

LABORATORY EQUIPMENT

MONITORING & SAMPLING Moisture contents: weekly Soil aggregate size: weekly Total C & N, HPC, ph, TEH: triweekly

MOISTURE RETAINING Soil Mixture Before Adjustment (%) After Adjustment (%) Moisture Retaining (%) Soil 66(8.4) 48(11.4) 72(11.7) Soil+bulking agents 71(10.0) 49(12.0) 68(11.5) Soil+humic (1%) Soil+humic (5%) 64(7.5) 60(6.7) 50(9.8) 53(8.4) 78(10.0) 87(9.2) Soil +humic(1%)+bulking agents Soil+humic(5%)+bulking agents 66(9.5) 62(7.0) 50(10.0) 54(8.1) 75(10.5) 86(7.2)

AGGREGATE SIZE Soil Mixture Aggregate Size Distribution (%) 4.0 mm 2.4 to 4.0 mm 1.4 to 2.4 mm Soil 88(4.9) 5(1.7) 2(3.20 Soil+bulking agents 76(3.9) 11(8.8) 4(3.4) Soil+humic (1%) Soil+humic (5%) 84 (3.4) 70 (11.2) 6 (1.9) 13 (4.5) 3 (1.2) 6 (3.8) Soil+humic(1%)+bulking agents Soil+humic(5%)+bulking agents 73(9.7) 75(8.7) 14(6.9) 13(4.4) 6(3.1) 4(3.0)

ph & C:N Soil Mixture Initial Week Values ph C:N Soil 7.6 7 Soil+bulking agents 7.4 14 Soil+humic (1%) 1 7.4 Soil+humic (5%) 1 7.2 Soil+humic (1%)+bulking agents Soil+humic (5%)+bulking agents Soil+additives (enzymes) Soil+additives (enzymes+biostimulants) 7.4 7.2 7.4-7.5 7.4-7.5 9 14 17 21 13-14 13-14 Soil+humic(1%)+additives(enzymes) Soil+humic(5%)+additives(enzymes+biostimulants) 7.1-7.4 7.0-7.2 17-19 16-24

HPC PROFILES 500 HPC Profiles (Bulking Agents and Humic Material) 400 HPC (10e6 /g) 300 200 Control Humic (5%) Bulking Agents BulkingAgents+Humic(5%) 100 0 0 3 6 9 12 Weeks

HPC PROFILES (Cont d) HPC Profiles (Soil Additives and Humic Material) HPC (10e6/g) 500 400 300 200 100 Control Humic(5%) Enzymes Enzymes+Biostimulants Enzymes+Humic(5%) 0 0 3 6 9 12 Weeks Enzymes+Biostimulants+Humic(5%)

HPC PROFILES (Cont d) HPC Profiles (Composting at 50 'C) HPC (10e6/g) 500 400 300 200 100 Manual Tilling Manual Tilling + Humic (5%) Forced Aeration Forced Aeration+Humic(5%) Manual Tilling + Bulking Agents Manual Tilling + Bulking Agents + Humic(5%) Forced Aeration + Bulking Agents 0 0 3 6 9 12 Weeks Forced Aeration + Bulking Agents + Humic (5%)

TEH PROFILES 5000 TEH (Bulking Agents and Humic Material) 4000 TEH (mg/kg) 3000 2000 1000 Control Humic (1%) Humic (5%) Bulking Agents Humic (1%) + Bulking Agents Humic (5%) + Bulking Agents 0 0 3 6 9 12 Weeks

TEH PROFILES (Cont d) TEH (Soil Additives + Humic Material) 5000 Control 4000 Humic (5%) TEH (mg/kg) 3000 2000 Enzymes Enzymes+Biostimulants Enzymes+Humic (5%) 1000 0 0 3 6 9 12 Weeks Enzymes+Biostimulants+Hu mic(5%)

TEH PROFILES (Cont d) 5000 TEH (Composting at 50 'C) Tilling + Control TEH (mg/kg) 4000 3000 2000 1000 Tilling + Humic (5%) Aeration + Control Aeration + Humic (5%) Tilling + Bulking Agents Tilling + Bulking Agents + Humic (5%) Aeration + Bulking Agents Aeration + Bulking Agents + Humic (5%) 0 0 3 6 9 12 Weeks

LAND TREATMENT SUMMARY No Treatment Tier I Objective (800 mg/kg) 1 Control 3,300 mg/kg @ 12 weeks 2 Humic @ 1% 1,200 mg/kg @ 12 weeks 3 Humic @ 5% Tier I @ 9 to 12 weeks 4 Bulking Agents @ 50% 1,000 mg/kg @ 12 weeks 5 2 + 4 Tier I @ 12 weeks 6 3 + 4 Tier I @ 6 to 9 weeks 7 Soil additives (enzymes) @ 0.1% 1,000 mg/kg @ 12 weeks 8 Soil additives (enzymes+biostimulants)@ 0.1% Tier I @ 12 weeks 9 3 + 7 Tier I @ 6 to 9 weeks 10 3 + 8 Tier I @ 3 to 6 weeks

STATIC-PILE COMPOSTING SUMMARY No Treatment Aeration Tier I Objective (800 mg/kg) 1 Control Tilling 2,700 mg/kg @ 12 weeks 2 Control Aeration 1,600 mg/kg @ 12 weeks 3 Humic @ 5% Tilling Tier I @ 6 to 9 weeks 4 Humic @ 5% Aeration Tier I @ 6 to 9 weeks 5 Bulking Agents @ 50% Tilling Tier I @ 9 to 12 weeks 6 Bulking Agents @ 50% Aeration Tier I @ 9 to 12 weeks 7 3 + 5 Tilling Tier I @ 6 to 9 weeks 8 4 + 6 Aeration Tier I @ 3 to 6 weeks

TREATMENT ALTERNATIVES SUMMARY Forced aeration outperformed tilling Higher temperature was better

HUMIC SUBSTANCES SUMMARY Improve soil quality Enhance microorganisms growth Enhance diesel biodegradation

BULKING AGENTS & SOIL ADDITIVES SUMMARY Improve humic substances performance Enhance microorganisms growth and diesel biodegradation Optimum dosages to be determined more thoroughly

ENHANCED BIODEGRADATION SUMMARY Shorter timeline for Tier I Simpler operation & optimization Cost factors to be considered Different hydrocarbons to be tested