Biodegradable and Degradable Plastics Biodegradation Testing in Aerobic Compost and Anaerobic Environments

Plastivida Brazil
June 10, 2008
Joseph P. Greene, Ph.D.
Professor California State University, Chico Chico, CA 95929-0789
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Agenda
Research Objectives Products Tested Results Compost Environment
Chico Green Yard Waste Chico In-vessel Manure Waste Vacaville In-vessel Food Waste Mariposa County In-vessel Municipal Solid Waste (MSW) Laboratory ASTM D-6400

Marine Water Environment Anaerobic Digestion Environment Laboratory Quality Tests for Contamination of Recycled Plastics Conclusions and Recommendations Questions 2

Objectives of Research
Evaluate
Performance, degradation rates and environmental impacts of degradable plastic products in commercially operated compost facilities and in simulated marine environments.

Testing
Bio-degradation
Compost environment: windrow, in-vessel, and laboratory locations Marine environment Anaerobic digestion

Environmental Safety Assessments

Fate and persistence of the by-products and toxicity resulting from the degradation

Mechanical and physical properties

Recycled plastics with contamination from degradable plastics
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What does Biodegradable Mean?

Can the microorganisms in the disposal system (composting, soil, anaerobic vessel) assimilate/utilize the carbon substrate as food source completely and in a short defined time period?

Environment soil, compost, waste water plant, marine Hydrolytic Oxidative Enzymatic Polymer chains with susceptible linkages Biodegradation: Only if all fragmented residues consumed by microorganisms as a food & energy source Define time and environment (disposal system)
Reference: Dr. Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Oligomers & polymer fragments

Complete

microbial assimilation

Specified time frame. No residual residues.

CO2 + H2O + Cell biomass

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Biodegradable versus Degradable Plastics

Biodegradable Plastics
Degraded by microorganisms in soil, compost, or marine environments. Made from natural materials, e.g.,corn, potato, polylactic acid, sugar cane, microbes, etc. Made from petroleum products, e.g. modified or polyesters. Compostable
Regulated by ASTM standards- will degrade in compost environment in less than 180-days. Does not leave any fragments in residue, does not have any heavy metals or toxins, and will support plant life.

Degradable plastics
Degraded by sunlight, oxygen, or microbes.
Oxodegradable, photo-degradable, starch-polyethylene plastics.

Can cause environmental problems.

Results in small fragments that can pollute compost, landfill, marine. Does not degrade as fast as compostable plastics, may leave small fragments in soil, may not have toxic residuals, may not support plant5 life.

DEGRADABLE = Major Environmental Problems

Designing products to be degradable or partially biodegradable causes irreparable harm to the environment

Degradable, biobased, single-use, disposable packaging and consumer

plastics, and plastic-paper combination products (non-durable goods) have serious environmental consequences.

Must ensure complete biodegradability in a short defined time frame

(determined by the disposal infrastructure like composting)

TIME --- ONE GROWING SEASON; MAYBE TWO DISPOSAL ENVIRONMENT Composting, anaerobic digestion plants, marine/oceans, soil

MUST ENSURE COMPLETE BIODEGRADABILITY IN THE SELECTED DISPOSAL ENVIRONMENT (as per ASTM test methods and specifications)
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Reference: Dr. Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Definitions
Degradable plastics
All plastics are degradable, though the mechanism is different. Oxidation: plastics degrade in oxygen environment. Anti-oxidants are added to polymers. UV light: plastics degrade in sunlight. Stabilizers are added to polymers. Heat: polymers can degrade under high temperatures. Stabilizers are added

Oxo-Degradable
Pro-degradents are added to increase the rate of oxidation and disintegration of plastics though NOT biodegradable since microorganisms do not consume them.

Biodegradable
Plastics degrade from microorganisms that consume material but time frame is not specified.
Can be biobased or petroleum based. Both can be consumed by microorganisms.

Compostable (Most complete definition)

Plastics that degrade from microorganisms that consume material in specified time frame and under specified environmental conditions.
7 Can be biobased or petroleum based. Both can be consumed by microorganisms.

Products Tested
Compostable (Certified by Biodegradable Polymers Institute- BPI)
PLA Cups, forks, spoons, knives, clamshell containers, lids, and straws Biobag trash bags Ecoflex Polyester bags PHA Bags Husky Eco Guard biodegradable bags Sugar Cane Bagasse plates, bowls, and containers.

Oxo-Degradable (NOT certified by Biodegradable Polymers Institute- BPI)

Natural Value Oxo-degradable Ecosafe Trash Bags Oxo Biodegradable Eco-friendly plastic bag UV-degradable plastic bags and soda can rings

Control
LDPE plastic trash bag Kraft paper Cellulose filter paper
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Commercial Compost Environment

Sites
Chico Green Yard Waste Chico In-vessel Manure Waste Vacaville In-vessel Food Waste Mariposa County In-vessel Municipal Solid Waste

Materials (Purchased at stores or on-line) Compostable: PLA lids, Biobag trash bags, Ecoflex Polyester bags, PHA Bags, Husky Eco Guard biodegradable bags, Sugar Cane Bagasse lids. Oxodegradable: Ecosafe Trash Bags, Eco-friendly plastic bag, UV-degradable plastic bags Controls: LDPE plastic trash bag and Kraft paper Tests Monitored visual disintegration and biodegradation of products after 30, 60, 90, and 180 day test intervals. Monitored temperature of air and compost, moisture percentage, pH, compost maturity, and % solids.
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Chico Green Yard Waste Compost

Pictures (120 days)

Compost pile

Incoming trash

Oxobiodegradable

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PLA Container

Biobag bag

Chico Green Yard Waste Compost

Results:
30 days: (Windrow)
No degradation: Oxo-biodegradable plastic trash bags Some degradation: Food waste and PLA cups, forks, spoons, knives, clamshell containers, lids, and straws, Sugar cane plates and lids, and Biobag trash bags.

120 days: (Windrow)

No degradation: Oxo-biodegradable plastic trash bags More degradation: Small fragments of PLA container and straw, and Biobag trash bags.

Full degradation: no visible fragments- PLA cups, forks,

spoons, knives, and lids; sugar cane lids and plates.
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In-vessel Manure and Food Waste Compost

Pictures (120 days)

In-vessel Compost pile

Turning row

Incoming MSW trash

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PLA Container

Biobag bag

In-vessel Manure and Food Waste Compost

Results
30 days (In-vessel)
Some degradation: Food waste and PLA cups, forks, spoons, knives, clamshell containers, lids, and straws, Sugar cane plates and lids, and Biobag trash bags.

120 days: (Windrow)

More degradation: Small fragments of PLA cups and container, and Biobag trash bags.

Full degradation: no visible fragments- PLA, forks,

spoons, knives, and lids; sugar cane lids and plates.

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NorCal Vacaville In-vessel Compost Pictures

In-vessel composting with polyethylene cover

Compost pile after 30 days

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NorCal In-vessel Compost Pictures

Corn starch plastic bag

Mirel PHA plastic bag

Ecoflex plastic bag

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Oxodegradable plastic bag

Oxodegradable plastic bag

UV-polyethylene plastic bag

NorCal Vacaville In-vessel Compost Pictures

PLA lids

Sugar can lids

Kraft paper

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Husky Eco-Guard plastic bag

LDPE plastic bags

NorCal Vacaville In-vessel Compost Pictures

Burlap sacks filled with samples

Compost pile after 30 days

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 Results

NorCal Vacaville In-vessel Food Waste Compost

30 days (In-vessel) September to October 2006
Some degradation: Food waste and PLA cups, forks, spoons, knives, clamshell containers, lids, and straws, Sugar cane plates and lids, and Corn starch trash bags.

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NorCal In-vessel Compost Pictures- 30 days

Corn starch plastic bag

Mirel PHA plastic bag

Ecoflex plastic bag

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Oxodegradable plastic bag

Oxodegradable plastic bag

UV-polyethylene plastic bag

NorCal Vacaville after 30 days Pictures

PLA lids

Sugar can lids

Kraft paper

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Husky Eco-Guard plastic bag

LDPE plastic bags

Vacaville In-vessel Food Waste Compost Pictures (180 days)

In-vessel Compost pile

Kraft paper

Sugar cane lids

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Compost temperature: 140 +/- 5F Moisture: 40-45%

Vacaville In-vessel Food Waste Compost Pictures (180 days)

Oxodegradable bag UV-degradable

LDPE stretch film control

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Vacaville In-vessel Food Waste Compost

Results
30 days (In-vessel) 60 days: (Windrow) 180 days: (Windrow) March 2007
No degradation: Oxo-biodegradable and UV degradable plastic trash bags; LDPE control. Some bio-degradation: Sugar cane lids and Kraft paper control though samples were very wet and fell apart when moved.

Full degradation: no visible fragments- PHA bag, Ecoflex bag, PLA lids, Biobag trash bags.
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Mariposa County In-vessel MSW Compost

Pictures

ECS In-vessel Compost Method

Inside chamber with samples

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Mariposa In-vessel Food Waste Compost

Oven Temperature: 60C for 3 days, 50C for 21 days % Moisture: > 50%

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Mariposa after 42 days Pictures

Corn starch plastic bag

Mirel PHA plastic bag

Ecoflex plastic bag

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Oxodegradable plastic bag

Oxodegradable plastic bag

UV-polyethylene plastic bag

Mariposa after 42 days Pictures

PLA lids

Sugar can lids

Kraft paper

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Husky Eco-Guard plastic bag

LDPE plastic bags

NorCal Vacaville Windrow Compost

Samples moved to windrow compost after 42 days for an additional 150 days

In-vessel Compost pile

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Compost temperature: 140 +/- 5F Moisture: 40-45%

Mariposa In-vessel Food Waste Compost

Results
42 days (In-vessel)
Some degradation: Food waste and PLA cups, forks, spoons, knives, clamshell containers, lids, and straws, Sugar cane plates and lids, and Biobag trash bags.

150 days: (Windrow) Identical to Vacaville result

No degradation: Oxo-biodegradable and UV degradable plastic trash bags; LDPE control. Some bio-degradation: Sugar cane lids and Kraft paper control though samples were very wet and fell apart when moved.

Full degradation: no visible fragments- PHA bag, Ecoflex bag, PLA lids, Biobag trash bags.

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Mariposa In-vessel (42 days) plus Vacaville Windrow Compost (150 days)

Pictures
Note: Same results as Vacaville Compost alone

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Kraft paper and sugar cane lids

Oxodegradable bags

Laboratory Biodegradation Compost

Materials
Kraft paper, Cellulose filter paper and low density polyethylene controls Oxo-biodegradable: Ecosafe and Eco-friendly plastic trash bags Compostable biodegradable products, i.e., PLA straws, Biobag trash bags, PHA bags, Ecoflex bags Biodegradable: Stalk Market sugarcane lids.

Method (Per ASTM D-5338)

Redesigned of laboratory procedure with
Improve the accuracy of CO2 measurement with LabView data acquisition system and computer control. CO2 scrubber, 50 psi pressure canister to supply moist air.

45-day test interval

Tests
Monitored carbon dioxide and oxygen levels for 45-days. Phytoxicity tests with tomato seeds. Regulated metals testing for Cd, Pb, and Co.

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Testing Methods
Laboratory Environment
ASTM 5338 Standards
Wet air void of CO2
Computer

CO2 or O2 Detector

Biogas 42 Jars at 50C for 45 days

Sampling process schematic.

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Laboratory Biodegradation Compost Pictures

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45-day Degradation Results

Material Biodegradation Conversion % Degradation rate g/day Results Pass Pass 61.91 64.03 61.22 61.12 60.47 60.14 1.69 1.70 2.19 0.014 0.014 0.014 0.014 0.013 0.013 0.000 0.000 0.000 Fail
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Cellulose positive control Kraft paper positive control PHA bag PLA straws Sugar cane plate Biobag trash bag Ecoflex bag Blank compost control Polyethylene negative control Oxodegradable bag

71.99

0.016

Pass Pass Pass Pass Pass ---Fail

Plant Growth Results

Material Average Germination 46.67 43.33 83.33 66.67 70 70 70 60 63.33 56.67 73.33 % Average Length, mm after 10-days 24.33 22.67 18.33 26.67 25 20 14 32.33 16 18.33 18.33 Average Germination Index 11.35 9.82 15.27 17.78 17.50 14.00 9.80 19.40 10.13 10.39 13.44 Average pH Results Compost control Cellulose control Avicell cellulose control Kraft paper control Polyethylene negative control PLA Container Sugar Cane lid Biobag trash bag PHA bag Ecoflex bag Oxo-degradable bag 8.50 8.80 8.70 8.40 8.63 8.50 8.77 8.63 8.83 8.60 8.80 Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass

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Regulated Metal Testing

Note: Maximum limit of Pb is 30 mg/kg, Cd is 17 mg/kg and Co is not regulated in the US.
Material Compost Cellulose Kraft Paper Polyethylene Biobag PLA straws Sugar Cane Ecoflex bag PHA bag Average Lead Concentration 0.02 mg/kg 0.02 mg/kg 0.02 mg/kg 0.02 mg/kg 0.02 mg/kg 0.02 mg/kg 0.02 mg/kg 0.02 mg/kg 0.02 mg/kg Result Pass Pass Pass Pass Pass Pass Pass Pass Pass Average Cd Concentration .001 mg/kg .001 mg/kg .001 mg/kg .001 mg/kg .001 mg/kg .001 mg/kg .001 mg/kg .001 mg/kg .001 mg/kg Result Pass Pass Pass Pass Pass Pass Pass Pass Pass
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Anaerobic Digestion at UC Davis

Materials
Kraft paper and low density polyethylene controls Oxo-biodegradable: Ecosafe and Eco-friendly plastic trash bags Biodegradable: Food waste and biodegradable products, i.e., PLA lids and straws, Biobag trash bags, PHA bags, Ecoflex bags, and Stalk Market sugarcane lids.

Methods
Per Dr. Zhangs research from U.C. Davis Place 1 g of sample in 1-L jar with 0.5L of water waste and food sludge at 50C. Duplicate test with new samples.

Tests

More research is needed.

Monitor biogas production over 30 day period.

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Anaerobic Digestion at UC Davis Pictures

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Anaerobic Digestion at UC Davis

Results: Duplicate trial: 45 days
Bio bag Clear
1.8 1.6 1.4 1.2 1 Biogas yield (L) 0.8 0.6 0.4 0.2 0 0 5 10 15 20 25 30 35 40 45
PLA, Ecoflex, Corn starch Oxo and UV degradable Food Waste PHA

Oxo bag Eco flex

Straws Food waste

Y ellowbag Cups

Digestion time (days)

Conclusions
Digestion occurs and biogas (CO2 and Methane) is generated for first 15 days. PHA DOES continues to generate biogas and thus digest anaerobically for the next 30 days. 39 PLA, Ecoflex, oxo-degradable, UV-degradable, and Kraft paper DO NOT generate biogas after 15 days.

Laboratory Marine Testing

Materials
Kraft paper and low density polyethylene controls Oxo-biodegradable: Ecosafe and Eco-friendly plastic trash bags Biodegradable: Biodegradable products, i.e., PLA straws, Biobag trash bags, PHA bags, Ecoflex bags, and Stalk Market sugarcane lids.

Methods (Based on ASTM D-6692 standards)

Place 30 mg of sample in jar with 100 ml of ocean water at 30C.
Ocean water was retrieved in July 2007 from Big Sur beach in California. Water was held at 5C until testing.

Tests
At 30 days weigh samples after 24 hours of drying in air and then replace water with fresh 100 ml and place in oven. At 60 days weigh samples after 24 hours of drying in air and then add fresh 40 ml and place in oven. At 90 days weigh samples after 24 hours of drying in air.
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More research is needed.

Laboratory Marine Testing Pictures

Experimental Set-up

Oxo-degradable 90 days

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PHA 30 days

PHA 90 days

Laboratory Marine Testing

Results
30 days in water
No degradation: Oxo-biodegradable and UV degradable plastic trash bags; LDPE control, Kraft paper control; PLA lids; Sugar cane lids; Biobag trash bags; Ecoflex bag, UV degradable soda rings.

Some degradation: PHA bag- 36% disintegration

60 days in water
No degradation: Oxo-biodegradable and UV degradable plastic trash bags; LDPE control, Kraft paper control; PLA lids; Sugar cane lids; Biobag trash bags; Ecoflex bag, UV degradable soda rings.

Some degradation: PHA bag- 60% disintegration

90 days:
No degradation: Oxo-biodegradable and UV degradable plastic trash bags; LDPE control, Kraft paper control; PLA lids; Sugar cane lids; Biobag trash bags; Ecoflex bag, UV degradable soda rings.
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Some degradation: PHA bag- 70% disintegration

Laboratory Quality Tests for Contamination of Recycled Plastics

Materials
Recycled PET, HDPE, LDPE Oxo-biodegradable plastic trash bags Biodegradable: PLA straws and Biobag trash bags

Method
Combine LDPE and Biobag bags at 0%, 10% and 20%. Combine HDPE and PLA at 0%, 5%, and10%. Heated plastic bags under IR heater and then chopped with grinder. Injection molded samples with dry blend of plastic.

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Laboratory Quality Tests for Contamination of Recycled Plastics

Processing
Injection molding tensile bars with 55 ton Arburg. Blow molding of bottles with Rocheleau R4 machine. Blown film with 1 Braybender extruder.

Testing
Quality
Melt index, density, moisture % Opacity, dart impact

Mechanical properties
Tensile modulus, elongation, and strength, impact

Samples were tested in batches of 5.

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Results Contamination of Recycled Plastics

Quality tests
PLA plastics at concentrations of 5 and 10 wt%
Negatively affected melt index, moisture content of LDPE. Decreased tensile strength and impact strength of LDPE.

Corn-starch based plastic bags at concentrations of 10 and 20 wt%

Oxodegradable plastics at concentrations of 10 and 20 wt% More research is needed.

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Negatively affected melt index, moisture content of HDPE. Decreased tensile strength and impact strength of HDPE.

Negatively affected melt index, moisture content of LDPE. Decreased tensile strength and impact strength of LDPE.

Results Contamination of Recycled Plastics

Mechanical tests
Tensile strength Material LDPE- neat LDPE 10%oxo LDPE 20% oxo LDPE 10% biobag LDPE 20% biobag HDPE- neat HDPE 5% PLA HDPE 10% PLA % increase -3 3 -1 -9 --4 -9 Ultimate Elongation % increase -23 29 12 -8 -20 100 Tensile Modulus % increase --10 -14 -14 -5 -4 -17 Impact strength % increase --2 -2 -4 -3 --31 -38
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Summary of Biodegradation Results

Compostable Plastics Environment Compost
(with proper moisture, oxygen, and temperature levels)

Meet ASTM D6400 standards

Oxodegradable Plastics Polyethylene

Yes- 100% biodegradable in 180 days No No, for most Yes, for PHA

No No

No No

Landfill
(with low moisture, oxygen, and temperature levels)

Marine
(with high moisture levels and low oxygen and temperature levels)

No

No

Anaerobic Digester
(with high moisture levels and low oxygen and temperature levels)

No, for most Yes, for PHA

No

No 47

Conclusions
Compostable materials degrade under commercial compost environments.
PLA container, Sugar cane lids, PHA bag, Ecoflex bag, and Husky Eco-Guard plastic bag completely degraded in commercial

Green yard waste, In-vessel compost systems, and Laboratory conditions Oxodegradable and UV-degradable plastics do NOT biodegrade in any compost environments. Oxodegradable and UV-degradable plastics may fragment into smaller pieces compost environments, but may also create more SEVERE environmental consequences.
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Conclusions
PHA degraded in marine and anaerobic digestion environments. Sugar cane degraded in anaerobic digestion environment and also in marine environment. PLA straws, Ecoflex bag, and Biobag did not disintegrate in marine environment and biodegraded slowly in anaerobic digestion environment.

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Conclusions
Biodegradable plastics are a contaminant to recycled plastics.
PLA and Biobag plastics at concentrations of 10 and 20 wt% can negatively impact melt index, moisture content, tensile and impact properties. Contamination of biodegradable plastics can be controlled like other contaminants to recycled plastics.

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 The research work will help the expanded use of compostable plastic materials for selected applications. The compostable materials should be certified as compostable by BPI and included in procurement standards. The compostable plastic materials should perform well in simple applications, e.g., food service ware, lawn and leaf refuse bags that have dry contents, grocery bags, department store bags, and pet bag products.

Recommendations

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Acknowledgements
The author would like to thank the following people and organizations who have helped develop this research work:
California Integrated Waste Management Board Mr. Edgar Rojas (CIWMB) and Mr. Mike Leaon (CIWMB) Dr. Cindy Daley (CSU, Chico), Dr. Ken Derucher (CSU, Chico), Dr. Gregory Kallio (CSU, Chico), Dr. Randy Miller (CSU, Chico), and Mr. Peter Natale (CSU, Chico) Dr. Fengyn Wang (NorCal Waste Systems), Chris Taylor (NorCal Waste Systems), and Mr. Greg Pryror (Jepson Prairie Organics). Mr. Steve Engfer (Mariposa County Waste Management).
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Questions?

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