BIOPLASTICS: TECHNOLOGY PRINCIPLES AND EXEMPLARS

Ramani Narayan ([email protected]) Department of Chemical Engineering & Materials Science Michigan State University

Biobased plastics hold great promise for achieving the goals of sustainable development and implementing the principles of industrial ecology. These bioplastics offer value in the sustainability/lifecycle equation by being part of the biological carbon cycle. This global carbon cycle vis--vis managing carbon efficiently and in an environmentally responsible manner will be discussed. Identification and quantification of biobased content uses radioactive C-14 signature. Life Cycle Assessment (LCAs) of these bioplastics often show reduced environmental impact and energy use when compared to plastics based solely on petroleum feedstocks. Biopolymers are synthesized by many types of living matter - plants, animals, and bacteria - and are an integral part of ecosystem function. Because they are synthesized by living matter, biopolymers are generally capable of being utilized by living matter (biodegraded), and so can be disposed in safe and ecologically sound ways through processes like composting, soil application, and biological wastewater treatment. Single use, short-life, disposable products can be engineered to be biboased and biodegradable. Biodegradability requires complete assimilation of the plastic by the microbial populations present in the selected disposal environment in a defined time frame as opposed to degradable or partially biodegradable. Therefore, bioboased content and biodegradability are essential elements for single use, short-life disposable packaging and consumer plastics. For durable, long life articles bioplastics needs to be engineered for long-life and performance, so biodegradability may not be an essential criterion. There are two basic routes to manufacture bioplastics. Direct extraction from biomass yields a series of natural polymer materials like cellulose, starch, proteins, fibers, and vegetable oils that can form the platform on which plastic products can be developed. Alternatively, the renewable resources/biomass feedstock can be converted to bio-monomers by fermentation or hydrolysis and then further converted by chemical synthesis to bioplastics like polylactic acid. Bio-monomers can also be microbially transformed to biopolymers like the polyhydroxyalkanoates plastics.. Vegetable oils offer another important carbon platform to polyols (precursors for polyurethanes, polyesters) and other functional monomers/macromers. Bioplastics will play an increasingly important role in a society moving towards a sustainable and environmentally responsible materials base. This presentation captures the principles of bioplastics technology and showcases technological and commercial successes of bioplastics. www.msu.edu/user/narayan www.ktmindustries.com; www.ecosynthetix.com www.bioplasticpolymers.com; www.bpiworld.org

BIOBASED MATERIALS 101 in Question Answer Format Ramani Narayan [email protected]

& MATERIALS SCIENCE

Q 1. Why biobased products (bioplastics) and how does using it help sustainable development?
Carbon is the major basic element that is the building block of polymeric materials -- biobased products, petroleum based products, biotechnology products, fuels, even life itself. Therefore, discussions on sustainability, sustainable development, environmental responsibility centers on the issue of managing carbon (carbon based materials) in a sustainable and environmentally responsible manner. Natural ecosystems manages carbon through its biological carbon cycle, and so it makes sense to review how carbon based polymeric materials fit into natures carbon cycle and address any issues that may arise. Global Carbon Cycle Biobased Products Rationale Carbon is present in the atmosphere as CO2. Photoautotrophs like plants, algae, and some bacteria fix this inorganic carbon to organic carbon (carbohydrates) using sunlight for energy.

Sunlight energy CO2 + H2O (CH2O)x + O2

Equation 1

Over geological time frames (>106 years) this organic matter (plant materials) is fossilized to provide our petroleum, natural gas and coal. We consume these fossil resources to make our polymers, chemicals & fuel and release the carbon back into the atmosphere as CO2 in a short time frame of 1-10 years (see Figure 1). However, the rate at which biomass is converted to fossil resources is in total imbalance with the rate at which they are consumed and liberated (>106 years vs. 1-10 years). Thus, we release more CO2 than we sequester as fossil resources a kinetics problem. Clearly, this is not sustainable, and we are not managing carbon in a sustainable and environmentally responsible manner. Biomass/Bio-organics CO2
BioProducts Industry 1 - 10 yrs > 106 years

Polymers, Chemicals & Fuels

Chemical Industry

Fossil Resources (petroleum, Natural gas)

Renewable Carbon CO2 , & Biomass

Green Materials & Products

Figure 1. Global carbon cycle sustainability driver However, if we use annually renewable crops or biomass as the feedstocks for manufacturing our carbon based polymers, chemicals, and fuels, the rate at which CO2 is fixed equals the rate at which it is

consumed and liberated this is sustainable and the use of annually renewable crops/biomass would allows us to manage carbon in a sustainable manner. Furthermore, if we manage our biomass resources effectively by making sure that we plant more biomass (trees, crops) than we utilize, we can begin to start reversing the CO2 rate equation and move towards a net balance between CO2 fixation/sequestration and release due to consumption. Thus, using annually renewable carbon feedstocks allows for: Sustainable development of carbon based polymer materials Control and even reduce CO2 emissions and help meet global CO2 emissions standards Kyoto protocol Provide for an improved environmental profile Q 2. How does one define a biobased material? Based on the discussions above, and the global carbon cycle one defines biboased materials/products as: Biobased material(s) (ASTM definition also in US Federal Government procurement definition) Organic material(s) in which the carbon comes from contemporary (new carbon vs old fossil carbon) biological sources

CO2 + H2O

(CH2O)x + O2

One must define organic materials since the term is used, and for this we adopt the accepted IUPAC (International Union of Pure and Applied Chemistry) nomenclautre Organic material(s) IUPAC terminology Material(s) containing carbon based compound(s) in which the carbon is attached to other carbon atom(s), hydrogen, oxygen, or other elements in a chain, ring, or three dimensional structures. Thus, to be classified biobased, the material must be organic and contain recently fixed (new) carbon present in biological sources Q 3. How does one distinguish between new (contemporary) and old (fossil) carbon identify biobased carbon? Q 4. How does one quantify biobased carbon content? Biobased materials may contain 100% bio-carbon (new carbon) or be mixed (physically, chemically, or biologically) with fossil carbon (old carbon). Therefore, one needs to define biobased content)
14

CO2 Solar radiation Biomass/biobased feedstocks CO2 ( CH2O)x

12

12 14

( CH2O)x > 10 years

6

14

C signature forms the basis to identify and quantify biobased content -- ASTM D6366
12

Fossil feedstocks -- Petroleum, Natural gas, Coal ( CH2)x ( CHO)x

12

Figure 2. Carbon-14 method to identify and quantify biobased content As shown in Figure 2, 14C signature forms the basis for identifying and quantifying biboased content. The CO2 in the atmosphere is in equilibrium with radioactive 14CO2. Radioactive carbon is formed in the upper atmosphere through the effect of cosmic ray neutrons on 14N. It is rapidly oxidized to radioactive 14 CO2, and enters the Earth's plant and animal lifeways through photosynthesis and the food chain. Plants

and animals which utilise carbon in biological foodchains take up 14C during their lifetimes. They exist in equilibrium with the 14C concentration of the atmosphere, that is, the numbers of C-14 atoms and nonradioactive carbon atoms stays approximately the same over time. As soon as a plant or animal dies, they cease the metabolic function of carbon uptake; there is no replenishment of radioactive carbon, only decay. Since the half life of carbon is around 5730 years, the fossil feedstocks formed over millions of years will have no 14C signature. Thus, by using this methodology one can identify and quantify biobased content. ASTM subcommittee D20.96 developed a test method (D 6866) to quantify biobased content using this approach. D6866 test method involves combusting the test material in the presence of oxygen to produce carbon dioxide (CO2) gas. The gas is analyzed to provide a measure of the products 14C/12C content and relative to the modern carbon-based oxalic acid radiocarbon Standard Reference Material (SRM) 4990c, (referred to as HOxII). biobased content, or gross biobased content Amount of biobased carbon in the material or product as fraction weight (mass) or percent weight (mass) of the total organic carbon in the material or product. Q 5. Why is biobased content on a carbon basis? This is because the rationale for using biobased products is that one can manage carbon emissions in a sustainable manner (the rate of carbon fixation by photosynthesis equals the rate of use and liberation to the atmosphere carbon neutral). Therefore, it makes sense to use carbon as the basis for the measure of biboased content and not oxygen or hydrogen or weight or mole. It is sustainable carbon management that is the driver for biobased products utilization. Q 6. Given a products elemental composition, how can one compute biobased content theoretically? Examples of biobased content determination The following examples illustrate biobased content determinations. 1. Product O is a fiber reinforced composite with the composition 30% biofiber (cellulose fiber) + 70% PLA (biobased material). The biobased content of Product O is 100% -- all the carbon in the product comes from biofeedstocks.. 2. Product P is a fiber reinforced composite with the composition 30% glass fiber + 70% PLA (biobased material. The biobased content of Product P is 100%, not 70%. This is because the biobased content is on the basis of carbon, and glass fiber has no carbon associated with it. However, in all cases, one must define biobased content and organic content. Thus, the biobased content of Product P is 100% but organic content is 70%, implying that the balance 30% is inorganic material. In the earlier example of Product O the biobased content is 100% and organic content is 100%. Thus this allows the end-user/customer to clearly differentiate between two 100% biobased products and make their choice on additional criteria looking at the LCA profile of the two products (using ASTM D 7075). 3. Product N is a fiber reinforced composite with the composition 30% biofiber (cellulose) + 70% polypropylene (petroleum based organic). Product N biobased content = 18.17% and not 30%. Again, biobased content is not based on weight (mass), but on a carbon basis i.e. amount of biobased carbon as fraction weight (mass) or percent weight (mass) of the total organic carbon.

Therefore, biobased content = 0.3*44.4 (percent biocarbon; cellulose)/0.7*85.7 (percent carbon in polypropylene)+ 0.3*44.4 (percent biocarbon) * 100 which computes to 18.17%. The justification and rationale for using carbon and not the weight or moles or other elements like oxygen, or hydrogen as the basis for establishing biobased content of products should now be very self evident. As discussed in earlier sections, the rationale for using biobased products is to manage carbon in a sustainable and efficient manner as part of the natural carbon cycle, therefore it makes sense to use carbon as the basis for determining biobased content. It is also fortituous that an absoloute method using 14C is available to measure the biobased carbon present in a material. Q 7. Have the theoretical calculations been validated by the ASTM test methods? The theoretical calculations presented earlier have been validated in experimental observations using ASTM D6866 and are in agreement within +/- 2%. Q 8. So where does biodegradability fit into this biobased equation? BIOBASED & BIODEGRADABLE -- Single use, short-life, disposable, controlled-life time products like packaging, disposable plastics, agricultural films, marine disposable must be engineered to be biodegradable/compostable, particularly if the disposal infrastructure is composting, anaerobic digestion, waste water treatment, soil, and similar biological infrastructures. In such a case, the product must meet ASTM D6400 Specification standard. BIOBASED & DURABLE products like soy polyurethanes for automotive and farm vehicles or Biofiber thermoplastic (like polypropylene) composites for industrial and automotive applications where biodegradability is not a required element for reasons of performance and durability and alternate methods of disposal needs to be designed. However, one needs to perform LIFE CYCLE ASSESSMENT (LCA) to document positive environmental attributes ASTM D7075 "Standard practice for evaluating and reporting environmental performance of biobased products". -- LCA TOOLS To incorporate life cycle costing analysis References (the above Q & A is excerpted from the following publications) 1. Biobased & Biodegradable Polymer Materials: Rationale, Drivers, and Technology Exemplars; ACS (an American Chemical Societypublication) Symposium Ser. 939, Bk Chapter 2006. 2. Presented at the National American Chemical Society, Division of Polymer Chemistry meeting, San Diego (2005); 3. R Narayan, Proceedings Plastics From Renewable Resources GPEC 2005 Global Plastics Environmental Conference - Creating Sustainability for the Environment, February 23-25, 2005 4. Plastics from Renewable Resources an E-live presentation to Society of Plastics Engineers (SPE) 2006

BIOBASED & BIODEGRADABLE PLASTICS - PRINCIPLES, CONCEPTS, & STANDARDS

Ramani Narayan [email protected]

& MATERIALS SCIENCE

www.msu.edu/user/narayan
Presented at 1st European BioPlastics Conference Brussels, Belgium Nov. 6 2006 Presented at SPE National Plastics Exposition (NPE 2006), Bioplastics 101 workshop Rationale, Drivers, Standards, and Technology for Biobased Materials; Ch 1 in Renewable Resources and Renewable Energy, Ed Mauro Graziani & Paolo Fornasiero; CRC Press, 2006
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

ACS (American Chemical Society publication) Symposium Ser. 939, Ch 18, pg 282, 2006

If you use any of the slides/materials, please reference authorship and affiliation (Ramani Narayan, Michigan State University) thank you

THIS PRESENTATION TEACHES:

WHY BIO? And how the use of bio based plastics promotes sustainable development and is it environmentally responsible? How does one identify and measure bio content?
theoretical and experimental bio content

Biodegradability --- the relationship between biobased (feedstock use) and biodegradability (what happens to product after use when disposed into the waste stream? What is the metrics for measuring biodegradability (under defined disposal conditions)? Degradable vs biodegradable?
Degradability is not an option!

LCA Principles

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

BIOBASED PRODUCTS WHY? WHAT VALUE IN THE SUSTAINABILITY LIFE CYCLE EQUATION

CARBON
is the major element that is the building block of biobased products, petroleum based products, biotech products, fuels, even life itself. SO THE ISSUE IS: MANAGING CARBON !!!!! IN A SUSTAINABLE & ENVIRONMENTALLY RESPONSIBLE MANNER
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

NATURE MANAGES CARBON BY:

BIOLOGICAL CARBON CYCLES

SO NEED TO BECOME PART OF NATURAL CARBON CYCLES

ISSUE MANAGING CARBON !!!!!

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

GLOBAL CARBON CYCLING Inorganic to Organic carbon conversion

CO2
(atmosphere)

Biomass Organic matter; Carbohydrates

Sunlight energy (CH2O)x + O2 photoautotrophs -- algae, plants, and some bacteria fix inorganic carbon to organic matter (carbohydrates) using sunlight as the energy CO2 + H2O

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

GLOBAL CARBON CYCLING THE ECO DRIVER CO2

Bio-chemical Industry

Biomass/Bio-organics

1 - 10 yrs

> 106 years

Polymers, Chemicals & Fuels

Chemical Industry

Fossil Resources (petroleum, Natural gas)

Renewable Carbon CO2 , & Biomass

New Biochemical Industry Small, entrepreneurial business

Green polymers & Chemicals

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

TERMINOLOGY

Biobased material(s) Organic material(s) in which the carbon comes from contemporary (non-fossil) biological sources

CO2 + H2O

(CH2O)x + O2

Organic material(s) IUPAC terminology

Material(s) containing carbon based compound(s) in which the carbon is attached to other carbon atom(s), hydrogen, oxygen, or other elements in a chain, ring, or three dimensional structure

Thus, to be classified bio or biobased, the material must be organic and contain recently fixed (new) carbon present in biological sources
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Standards -- Identify & Quantify Biobased Content

How does one distinguish between new (contemporary) and old(fossil) carbon identify biobased carbon? How does one quantify biobased carbon content?

14CO Solar radiation 2 12CO 2

Biomass/Bio-organics

(12CH2O)x

(14CH2O)x
> 106 years

C-14 signature forms the basis of Standard test method to quantify biobased content (ASTM D6866)
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Fossil Resources (petroleum, natural gas, coal)

(12CH2)n

(12CHO)x

BIOBASED CONTENT
Biobased materials may contain 100% bio-carbon (new carbon) or be mixed (physically, chemically, or biologically) with fossil carbon (old carbon). Therefore, one needs to define biobased content
biobased content, or gross biobased content

Amount of biobased carbon in the material or product as

fraction weight (mass) or percent weight (mass) of the total organic carbon in the material or product.

NOTE: Only on a carbon basis, not weight or mole or any other measure. This is because the rationale for using biobased products is that one can manage carbon emissions in a neutral fashion (the rate of carbon fixation by photosynthesis equals the rate of use and liberation to the atmosphere carbon neutral

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

BIOBASED CONTENT -- EXAMPLES

Product O is a fiber reinforced composite with the composition 30% biofiber (cellulose fiber) + 70% PLA (biobased material) Product P is a fiber reinforced composite with the composition 30% glass fiber + 70% PLA (biobased material Product N is a fiber reinforced composite with the composition 30% biofiber (cellulose) + 70% polypropylene (petroleum based organic) 1. Product O biobased content = 100% 2. Product P biobased content = 100%; organic content only 70% 3. Therefore must define biobased content and organic content! 4. Product N biobased content = 18.5% -- not 30%!!!! Because biobased content is on a carbon basis
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

O.3*45.5/0.3*45+0.7*85.7 = 18.5%

MATERIALS DESIGN PRINCIPLES FOR THE ENVIRONMENT

BIOBASED & BIODEGRADABLE Single use, short-life, disposable, controlled-life time products Packaging, disposable plastics, agricultural films, marine disposable BIOBASED & DURABLE (where biodegradability is not a required element for Soy polyurethanes for automotive and farm vehicles Biofiber composites for industrial and automotive Perform LIFE CYCLE ASSESSMENT (LCA) to document positive environmental attributes ASTM D7075 "Standard practice for evaluating and reporting environmental performance of biobased products". -- LCA TOOLS To incorporate life cycle costing carbon credits; emissions trading
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

reasons of performance and durability and alternate methods of disposal needs to be designed )

MATERIALS DESIGN PRINCIPLES FOR THE ENVIRONMENT

FEEDSTOCK

BIOBASED OR PETROCHEMICAL Energy efficiency Reduce environmental impacts BIODEGRADABILITY

PRODUCT MANUFACTURE

Transform into Useful Product

ULTIMATE DISPOSABILITY

LIFE CYCLE ASSESSMENT LCA ASTM D7075

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

What does Biodegradable Mean?

Can the microorganisms in the disposal system (composting, soil, anaerobic digestor) 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)
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Oligomers & polymer fragments

Complete

microbial assimilation

defined time frame, no residues!!!

CO2 + H2O + Cell biomass

Integration of biodegradable plastics with disposal infrastructures Marine environment

Anaerobic digestion facility

COMPOSTING COMPOSTING FACILITY FACILITY

Biodegradable Biodegradable Plastics Plastics INCINERABLE

Paper-biopolymer composite

RECYCLING RECYCLING FACILITY FACILITY

recycling polymeric carbon back to soil

LAND APPLICATION

WASTE TO ENERGY WASTE TO ENERGY FACILITY FACILITY ENERGY

RECYCLED PRODUCTS

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Countrys typical MSW distribution by weight

Misc. 2%

Tins & Metal 4% Bottles & Glass 7% Plastics 16%

54% Biowastes Vegetables & perishables

Paper & Cardboard Textiles 13% 4%

COMPOSTABLES
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

COMPOSTING & THE ENVIRONMENT

COMPOSTING IS AN ECOLOGICALLY AND ENVIRONMENTALLY SOUND APPROACH TO TRANSFERRING BIODEGRADABLE WASTE (INCLUDES THE BIODEGRADABLE PLASTICS) TO USEFUL PRODUCT

COMPOSTING IS BIOLOGICAL RECYCLING OF CARBON

COMPOST USE REDUCES CHEMICAL INPUTS, SUPRESSES CROP DISEASES, REPLENISHES ORGANIC CARBON, INCREASES WATER & NUTRIENT RETENTION, IMPROVES SOIL PRODUCTIVITY SUSTAINABLE AGRICULTURE SCIENCE & ENGINEERING OF COMPOSTING, HOITNIK & KEENER, EDS. 1993 Narayan -- Biodegradation of polymeric materials during composting, p. 339
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

How does one quantify biodegradability or bioassimilation? METRICS FOR BIODEGRADABILITY?

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

METRICS FOR BIODEGRADABILITY?? Microorganisms extract chemical energy for use in their life processes by the aerobic oxidation of glucose and other utilizable substrates BIODEGRADBLE PLASTICS, food waste, paper, forest residues biological matter AEROBIC Glucose + 6 O2 ANAEROBIC Glucose 6 CO2 + 6 H2O; G0 = -686 kcal/mol

2 lactate; G0 = -47 kcal/mol

CO2 is a quantitative measure of biodegradation/bioassimilation

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

More Biodegradation/Bioassimilation Facts

The aerobic oxidation process (a highly specialized cellular phenomenon) requires the participation of three metabolically interrelated processes: 1. Tricarboxylic acid cycle (TCA cycle) 2. Electron transport 3. Oxidative phosphorylation All of the processes take place inside the cell
For these processes to occur, the substrates needs to be transported inside the cell
So molecular weight, hydrophobic/hydrophilic balance, other molecular and structural features govern transport across cell membrane into the cell for utilization of the C-substrate.

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

O2

CO2

100 90 80 70 60 50 40 30 20 10 0

% C conversion to CO2

biodegradation curve biodegradation degree 65%

Compost & Test Materials

lag-phase

degradation phase

plateau phase

12

16

20

24

28

32

36

40

44 time (d)

QUESTIONS: Increase time period from 180 days to 365 days? how? Should we do it?, microbial activity issues, can we do a acclimatizing step Radiolabelling methodology longer duration, can use active compost environment
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Cradle to Cradle Concept for Material Design

(Integration of Biodegradable Materials with Disposal Infrasructures) TEST METHOD ASTM D5338; ISO14855 1 & 2 ISO16939 (disintegration) ASTM D6340 C-14 SPECIFICATIONS ASTM D6400; EN 13432 ISO 17088 ASTM D6868 paper coatings COMPOSTING COMPOSTING FACILITY FACILITY ASTM D 5988 Soil Soil Mulch film Mulch film Agriculture appl Agriculture appl ASTM D 6691,6692 D 7021 specification Marine & fresh water

Biodegradable Biodegradable Materials Materials

Anaerobic digestion biogas energy plant ASTM D5511 ISO 15985

recycling polymeric carbon back to soil

LAND APPLICATION

Waste water Waste water treatment treatment facility facility ASTM D5271 ISO 14851/14852

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

BIODEGRADABILITY Define Time complete and short (one growing season) Define Disposal Environment like composting Degradability is not an option!

Problems with Degradables Toxic Chemicals Transport

plastic pieces can attract and hold hydrophobic elements like PCB and DDT up to one million times background levels. As a result, floating plastic is like a poison pill -endocrine disruptors
From Algalita Marine Research Foundation
www.algalita.org/pelagic_plastic.html

PCBs, DDE, and nonylphenols (NP) were detected in high concentrations in degraded polypropylene (PP) resin pellets collected from four Japanese coasts. Plastic residues function as a transport medium for toxic chemicals in the marine environment.
Mato et al Environ. Sci. Technol. 2001, 35, 318-324

Narayan

Microparticulate Plastics* Microparticulate Plastics*

Plastic micro- and nanoparticles

- From products such as hand srub - From processes such as powder coating - Deterioration of photo and enviro

degrading plastic materials

Concerns Relating to Microparticles

- Concentration and transfer of pollutants up the food chain - Invasive species transport

Piece of plastic washed ashore on a remote Mozambican island, complete with colonists
Narayan

*SLIDE BY ANTHONY ANDRADY, RTI

Colonized Plastic Particle attracts and transports food

Captain Charles Moore Algalita Marine Research Foundation

Major Problems/Issues with Degradable Materials/Products (contd.)

Plastic debris around the globe can erode (degrade) away and end up as microscopic granular or fiberlike fragments, and that these fragments have been steadily accumulating in the oceans fragments come from several sources, the researchers suggest. These include mechanical erosion of nondegradable plastic bottles and packaging, nondegradable parts of biodegradable plastics, and plastic pieces used as abrasives in cleaning agents.
Science 304, 838, 2004
Narayan

FLOTSAM Lab experiments show that marine animals consume microscopic bits of plastic, as seen here in the digestive tract of an amphipod. Science 2004

Major Environmental Problems

Designing products to be degradable or partially biodegradable causes irreparable harm to the environment Degraded products may be invisible to the naked eye. However, out of sight does not make the problem go away

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)

Narayan

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

Global Standards for Biodegradability

Composting Assn UK

USA
Coming Soon!

www.bpiworld.org
Memorandum of Understanding Cross Certification Program

BPS JAPAN

DIN CERTCO GERMANY

BPS Brazil

Common ISO Standard for Biodegradable Plastics

EBPA Taiwan

KBPA Korea

BPS China

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

MATERIALS DESIGN PRINCIPLES FOR THE ENVIRONMENT

LIFE CYCLE ASSESSMENT LCA ASTM D7075

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Life Cycle Assessment Framework

Goal & Scope Definition

ISO 14041

Direct Applications: Product development & Improvement Strategic Planning Communication Public Policy Marketing Other
ISO 14043

Inventory Analysis
ISO 14042

Interpretation
Conclusions, recommendations, and reporting

Impact Assessment

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Components in a product life cycle Inputs

Energy Raw material acquisition Manufacturing and Formulation Distribution and Transportation Use/Reuse/Maintenance Waste Management

Outputs
Airborne emissions Water effluents Solid Wastes Other releases Usable products

Raw Materials and Products

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Life Cycle Impact Assessment

RELATED EMISSIONS NOx, VOCs, CH2O (and others) (+21) CCl4, CCl2F2, CFC12, CH3Br (+3) PM10, PM2.5 (and others), SO2, NO2 As, Cr, Dioxins, Pb, Hg (+20) CO2, CH4, N2O, CF4 (+8) 3NOx, P, NO3 , PO4 , NH3, N2O (+6) Mg, Zn, Ni, V, Cd (+20) SO2, NO2, H2S, HCN HCL, HF, NH3 (+1)

IMPACT CATEGORY photochemical smog ozone depletion human health criteria human health (non)cancer global warming eutrophication ecotoxicity 1 acidification
1,2 1

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Impact Categories and Methodology

IMPACT CATEGORY POTENTIAL ozone depletion (ODP) global warming (GWP) acidification1(AP) eutrophication1,2(EP) photochemical smog1(SP) human health cancer (HP) human health noncancer (HP) human health criteria (CP) ecotoxicity (EP) fossil fuel use (FP) land use1 (TED) water use IMPACT CATEGORY POTENTIAL BEES DEFINITION
grams of CFC-11 with the same ozone depletion potential as one gram of inventory flow i grams of carbon dioxide with the same heat trapping potential over 100 years as one gram of inventory flow i millimoles of hydrogen ions with the same potential acidifying effect as one gram of inventory flow i grams of nitrogen with the same potential nutrifying effect as one gram of inventory flow i grams of nitrogen oxides with the same potential for smog formation as one gram of inventory flow i grams of toluene with the same potential human health effects as one gram of inventory flow i grams of toluene with the same potential human health effects as one gram of inventory flow i microDALYs per gram of inventory flow i grams of 2,4-D with the same ecological toxicity potential as one gram of inventory flow i MJ input requirement increase per kilogram of consumption of fossil fuel i U.S. T&E Species density (in T&E Species count per m2) Not defined in BEES

Scope:

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Example GLOBAL WARMING POTENTIAL CALCULATION global warming index = i mi x GWPi, Where mi = mass (in grams) of inventory flow i, and GWPi = grams of carbon dioxide with the same heat trapping potential over 100 years as one gram of inventory flow i, as listed in Table
Table 2.1 BEES Global Warming Potential Characterization Factors Flow (i) GWPi(CO2-equivalents) Carbon Dioxide (CO2, fossil) 1 Carbon Tetrafluoride (CF4) 5700 CFC 12 (CCl2F2) 10 600 Chloroform (CHCl3, HC-20) 30 Halon 1301 (CF3Br) 6900 HCFC 22 (CHF2Cl) 1700 Methane (CH4) 23 Methyl Bromide (CH3Br) 5 Methyl Chloride (CH3Cl) 16 Methylene Chloride (CH2Cl2, HC-130) 10 Nitrous Oxide (N2O) 296 Trichloroethane (1,1,1-CH3CCl3) 140hg
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Example --HUMAN HEALTH INDEX CALCULATION Human health Index = i mi x HPi, Where mi = mass (in grams) of inventory flow i, and HPi = grams of toluene with the same potential human health effects as one gram of inventory flow i.
Table 2.7 Sampling of BEES Human Health Characterization Factors Flow (i) HPi (tolueneequivalents) Cancer--(a) Dioxins (unspecified) 38 292 661 685 580 Noncancer--(a) Dioxins (unspecified) 2 286 396 218 965 Cancer--(a) Diethanol Amine (C4H11O2N) 2 532 000 000 Cancer--(a) Arsenic (As) 69 948 708 Cancer--(a) BenzoCancer--(a)pyrene (C20H12) 34 210 977 Noncancer--(a) Mercury (Hg) 19 255 160 Noncancer--(w) Mercury (Hg+, Hg++) 18 917 511 Cancer--(a) Carbon Tetrachloride (CCl4) 17 344 285 Cancer--(w) Carbon Tetrachloride (CCl4) 16 483 833 Cancer--(a) Trichloropropane (1,2,3-C2H5Cl3) 3 587 000 Cancer--(a) Chromium (Cr III, Cr VI) 3 530 974 Cancer--(a) Dimethyl Sulfate (C2H6O4S) 2 976 375 Noncancer--(a) Lead (Pb) 1 501 293 Cancer--(a) Lead (Pb) 748 316 Cancer--(a) Ethylene Oxide (C2H4O) 650 701

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Life Cycle Impact Assessment

LCI Emissions Assign Emissions to Impact Categories Find potential of assigned emissions using equivalents Calculate Final Impact Index

X index

m i XP i

LCI based Emissions/Consumptions

Ozone Depletion Global Warming Acidification Eutrophication Photochemical Smog Human Health Cancer Human Health Noncancer Human Health Criteria Ecotoxicity Fossil Fuel Use Land Use Water Use

OP: CFC-11 GWP: CO2 AP: H+ EP: P or N SP: NOx HTP to Benzene HTP to Toluene CP: Disability Adjusted Life Years EP: 2, 4-Dichlorophenoxy AceticA FP: MJ/consump of fuel/unit of prod. TED: T&E density

Ozone Depletion Global Warming Acidification Eutrophication Photochemical Smog Human Health Cancer Human Health Noncancer Human Health Criteria Ecotoxicity Fossil Fuel Use Land Use Water Use

Ramani Narayan, Michigan State University, www.msu.edu/~narayan

Life Cycle Impact Assessment: Normalized PE and Starch Foam LCIA

1.20 1.00 PE Foam (PF) Starch Foam (SF)

Normalized Values

0.80 0.60 0.40 0.20 0.00 GWP AP EP CP HP SP OP ECP

Impact Categories
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

BEES SCORING GRAPHIC

TRACI The Tool for the Reduction and Assessment of Chemical and Other Environmental Impacts Jane C. Bare EPA

ASTM standard for

Multiattribute Decision Analysis (E 1765). ASTM International standard life-cycle cost method (E 917),
Ramani Narayan, Michigan State University, www.msu.edu/~narayan