Ramani Narayan, is University Distinguished Professor at Michigan State University in the Department of Chemical Engineering & Materials Science He

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1 Ramani, is University Distinguished Professor at Michigan State University in the Department of Chemical Engineering & Materials Science He has 130 refereed publications in leading journals to his credit, 25 issued patents, and several pending patents, edited three books and one expert dossier in the area of bio-based polymeric materials. His research encompasses design & engineering of sustainable, biobased products, biodegradable plastics and polymers, biofiber reinforced composites, reactive extrusion polymerization and processing, studies in plastic end-of-life options like biodegradation and composting. His research involves developing carbon and environmental footprint of biobased and biodegradable plastics and products using biocarbon content analysis (ASTM D6866) and LCA (life cycle assessment) methodology respectively. Under his supervision, 20 students have obtained their Master s degree, 15 students their Ph.D. degrees and six are working towards their Ph.D. He has major research programs with industry and serves as consultant for several companies. He serves as the Scientific Chair of the Biodegradable Products Institute (BPI), North America He served on the Board of Directors of ASTM International ( a premier international standards setting organization and currently chairs the committee on Environmentally Degradable Plastics and Biobased Products (D20.96) and the Plastics Terminology committee D He serves as the USA technical expert to ISO (International Standards Organization) TC 61 on Plastics, and serves as the Chairman of ISO TC 61 SC 1 on Terminology. He is Convener of working group 7 of ISO TC 120 SC 4 on Packaging and the Environment He has testified before U.S. congressional hearings on the biodegradable and biobased plastics issues. He serves on the Board of Directors of Northern Technologies International ( ) a $100 million publicly traded micro cap company, and on the Technical Advisory board of Tate & Lyle ( a world leading manufacturer of renewable food and industrial ingredients He has won several awards: Named MSU University Distinguished Professor in the highest honor that can be bestowed on a faculty member by the university. Those selected for the title have been recognized nationally and internationally for the importance of their teaching, research and public service achievements; Governor s (State of Michigan) University Award for commercialization excellence; University Distinguished Faculty Award, 2006 awarded to 10 faculty from amongst all the faculties at Michigan State University; 2005 Withrow Distinguished Scholar award -- awarded to one faculty in the MSU College of Engineering based on exemplary research accomplishments, national & international recognition; Fulbright Distinguished Lectureship Chair in Science & Technology Management & Commercialization (University of Lisbon; Portugal); First recipient of the William N. Findley Award for significant contributions to the application of new technologies within the scope of ASTM Committee D20 on Plastic; Award of Excellence from ASTM committee D20 on Plastics for exemplary technical contributions, and valued leadership, 2006; the ASTM award of merit, the highest award given by the society to an individual member and comes with the title of Fellow. The James Hammer Memorial Lifetime Achievement Award, 2006 for outstanding leadership, and research accomplishments in the field of Degradable Polymers from the BioEnvironmental Polymer Society (BEPS). Research and Commercialization Award sponsored by ICI Americas, Inc. & the National Corn Growers Association. He is a successful entrepreneur having been responsible for commercializing several technologies. He developed poly(lactic acid) materials technology and conducted engineering scale-up studies for Cargill Inc. The technology is currently being commercialized by NatureWorks LLC ( ). He developed biodegradable, modified starch ester thermoplastics technology, covered by three patents, which was acquired by a major Japanese corn wet miller, Japan Corn Starch (JCS). Corn Products, with net sales of $2.3 billion licensed three of his patents (on modified starch, and starch-polyester composite resins) to commercialize the technology through a JV with chemical giant BASF in Brazil ( Biofoam sheets for cushion packaging and insulation material is being marketed under the trade name GreenCell by KTM Industries ( biodegradable and recycling friendly starch based nanoparticle adhesives through Eco Synthetix ( biopolyester and cellulosic based resins for biodegradable/compostable films, molded products, and engineering plastics through BioPlastic Polymers & Northern Technologies( a $100 million NASDAQ traded company; and modified polysaccharides for drug delivery through BioPolymer Innovations ( He is also developing and commercializing technology for manufacturing new biopolyesters, and polyols that find application in polyurethanes and polyester resins products using vegetable and algal oil platforms. He is involved with setting up a biorefinery in conjunction with a Michigan agribusiness, Zeeland biobased products ( producing advanced biofuels, biomoners and plastic products in addition to the traditional food and feed products.

2 May 11, 2010 RN GOING GREEN --Understanding Biobased & Biodegradability Concepts BUT Look out for GREEN WASHING Presentation at Midwest BioPolymers & Biocomposites Workshop; Iowa State University Ramani University Distinguished Professor If you use any of the slides/materials, please reference authorship and affiliation (Ramani, Michigan State University) thank you Copyright Ramani

3 Carbon footprint reduction strategy using bio content WHY BIO? Value Proposition for Biobased (Biomass/Renewable) Products Switching the origins of a product s CARBON from petro/fossil to bio reduces the carbon footprint: Reducing heat trapping CO 2 emissions -- Minimizing global warming/climate change problems Using (renewable) biomass feedstock as opposed to petro/fossil feedstock energy/environmental security Economic development empowering rural farm, forestry and allied manufacturing industry 2

4 Carbon footprint reduction strategy using bio content Carbon footprint (global warming impact category, GWP): MATERIAL/PRODUCT CARBON FOOTPRINT Impact of replacing completely or in part the petro/fossil carbon with bio carbon the origins of the carbon H 2 C PE CH 2 n CH C CH 3 O PLA O n C a H b O c X d a,b,c,d are set positive integers; and X = N, S, C C O CH 2 CH 2 O O O PET n Ramani, Michigan State University 3

5 Carbon footprint reduction footprint strategy (global using bio content warming impact category, GWP): PROCESS CARBON FOOTPRINT Impact of converting feedstock to product Carbon emissions from all stages of unit operations to convert the selected C- feedstock (petro or bio/renewable) to product Life cycle Inventory analysis -- LCI Impact on the environment of the carbon emissions from the conversion process process global warming potential (GWP) Life Cycle Impact assessment -- LCIA Environmental Footprint Carbon footprint + other impact footprint categories like human health, ozone depletion, eutrophication, acidification, photochemical smog, etc Ramani, Michigan State University 4

6 ORIGINS OF CARBON IN PRODUCT Material and Process Carbon Footprint POLYETHYLENE POLYESTERS Oil Naptha Ethylene Ethylene oxide Ethylene Glycol Bio/renewable feedstock Corn, sugarcane, cellulosics Veg oils Ramani, Michigan State University Sugar monomers EtOH PLA, PHA BIO monomers, products

7 Carbon Value footprint Proposition reduction strategy using bio for content bio carbon vs petro/fossil carbon sunlight energy CO 2 +H 2 O (CH 2 O) X +O 2 photosynthesis 1-10 years Biomass, Ag & Forestry crops & residues NEW CARBON 1-10 years USE for materials, chemicals and fuels > 10 6 YEARS MATERIAL CARBON FOOTPRINT Fossil Resources (Oil, Coal, Natural gas) -- OLD CARBON Rate and time scales of CO 2 utilization is in balance using bio/renewable feedstocks (1-10 years) as opposed to using fossil feedstocks 6

8 Carbon footprint reduction strategy using bio content Material Carbon Footprint What is the impact of the material/product s carbon footprint on the environment? 100 Kg of polyethylene will result in net?? Kg of CO 2 released into the atmosphere Based on petro carbon vs bio carbon 100 Kg of polyester (PET )acid will results in net?? Kg CO 2 release into the atmosphere based on how many petro carbons vs bio carbons H 2 C CH 2 n C C O CH 2 CH 2 O PE O O PET n Ramani, Michigan State University 7

9 Material Carbon Footprint 350 Kg of CO 2 per 100 Kg resin kg of CO 2 emissions reduction for every 100 kg of PE resin in which the petro carbon is replaced with bio carbon ZERO CARBON FOOTPRINT 0 PE/PP PET Bio-PE/PET/PLA Ramani, Michigan State University

10 PLASTICS LANDFILLED NO CO 2 RELEASE -- SCENARIO Material Carbon Footprint Kg of CO2 per 100 kg of resin PE/PP BIO-PE Zero footprint -- product recycled, no release of gas to the environment Ramani, Michigan State University

11 Carbon footprint reduction strategy using bio content Material carbon footprint calculations PET exemplar Material Carbon Footprint % CO2 reductions by switching to biobased PET (achievied by partial replacemnt of the petro carbon of the glycol component with bio carbon -- corresponds to 31.5% by weight of the bio-renewable glycol component Ramani, Michigan State University PET BIO-PET 1 10

12 Carbon Communicating footprint reduction strategy and using presenting bio content CO 2 emissions reduction data material carbon footprint Considering that the world wide use of PET resin for bottles and fiber is 37.5 million metric tons, this first step of replacing the glycol petro carbon with bio carbon offers an annual CO2 reduction of million metric tons. To visualize this CO2 reduction in practical ready-to-understand terms the following equivalency applies (equivalency calculator): Eliminate CO2 emissions from driving 3 million passenger vehicles each year Eliminate CO2 emissions from consuming 1,951,191,82 gallons of gasoline each year Eliminate CO2 emissions from consuming 40 million barrels of oil each year Eliminate CO2 emissions from using electricity in 2,384,189 homes each year Ramani, Michigan State University GHG, equivalency calculator; 11

13 Carbon footprint reduction strategy using bio content Measurement of bio (carbon) content the Principle 14 CO 2 Solar radiation Biomass/Bio-organics 12 CO 2 ( 12 CH 2 O) x ( 14 CH 2 O) x NEW CARBON C-14 signature forms the basis of Standard test method to quantify biobased content (ASTM D6866) Cosmic radiation 14 N 14 C 14 CO 2 12 CO 2 > 10 6 years Fossil Resources (petroleum, natural gas, coal) ( 12 CH 2 ) n ( 12 CHO) x OLD CARBON, ACS (an American Chemical Society publication) Symposium Ser.939, Chapter 18, pg 282,

14 Carbon footprint reduction strategy using content Measurement of biobased (carbon) content ASTM D6866 C-product combusted to CO 2 14 C/ 12 C ratio is compared directly with a oxalic acid radiocarbon standard reference material (SRM 4990c) that is 100% new (bio) carbon dpm/g is the absolute value of the primary oxalic acid standard (SRM 4990b) actually dpm/g (0.93 of of the reference standard) to correct for the post C injection into the atmosphere Contains concentration of 1.2 x % of C-14 isotope equivalent to 100% bio carbon content IMPORTANT NOTE: To calculate percent bio carbon present in product multiply the experimental biobased content (from ASTM D6866) with the percent total organic carbon (TOC) (as determined by standard elemental analysis) 13

15 COMPLEX MATERIALS Beverage bottle composed of three components, the bottle, the cap, and sleeve Computer composed of multiple components organic and inorganic materials Automobile composed of multiple components organic and inorganic materials more complex Many more products in between these complexities

16 Biobased (Carbon) content of complex materials Biobased carbon content of complex product (BCC product ) comprising i constituents whose biobased and organic carbon content can be experimentally determined equals: W i * BCC i * OCC i / W i * OCCi W i = mass of the ith component BCC i = biobased carbon content of ith component OCCi = organic carbon content of the ith component Minimum organic carbon content of constituent i (OCC i ) = 30% Minimum biobased carbon content of constituent I (BCC i ) = 20% R,, MSU, 2010 www. biopreferred.gov; Public meeting, Complex Assemblies Forum Feb 24, Riverside, CA

17 Carbon Terminology: footprint reduction strategy using bio content BIOBASED (BIOMASS OR RENEWABLE BASED) Biobased (Biomass or Renewable) based Materials Organic material/s containing in whole or part biogenic carbon (carbon from biological sources) Organic Material/s -- 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 (IUPAC nomenclature) Biobased (carbon) Content -- The bio content is based on the amount of biogenic carbon present, and defined as the amount of bio carbon in the plastic as fraction weight (mass) or percent weight (mass) of the total organic carbon in the plastic. (ASTM D6866) % bio or biobased content = Bio (organic) carbon/total (organic carbon) * 100 % biobased content of complex products = W i * BCC i * OCC i / W i * OCCi ASTM D6866 Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis 16

18 Take Home Message Use bio (carbon) content analysis (ASTM D6866) to document verifiable CO 2 reductions Intrinsic material carbon footprint reductions and the rationale for switching from a petro/fossil carbon feedstock base to a bio/renewable carbon feedstock Remember LCA methodology provides the process carbon and environmental footprint not material carbon replacement footprint

19 Carbon footprint reduction strategy using bio content Biodegradability A misused and abused term Using biodegradability as an end-of-life strategy to completely remove single use short life disposable products from the environmental compartment in a safe and efficacious manner via microbial assimilation (microbial food chain) Disposal environment (like composting, anaerobic digestor, marine, landfill?? Define time to complete biodegradation Degradable, partial biodegradable not acceptable serious health and environmental consequences 18

20 TERMINOLOGY ENVIRONMENTAL BIODEGRADABILITY END-OF-LIFE scenario Biodegradability (Environmental) is a measure of the microbial utilization of (carbon) substrates in the selected environment Biodegradability must be Complete otherwise serious consequences Biodegradability in a measure, short time period for composting it is 180 days BIOMATERIALS Biomedical applications Refers to: Any material (metal, plastic, ceramic) implanted in the body -- design and engineering considerations different; biodegradability considerations different Biodegradability can be partial with break down products assimilated by the body, and the remaining polymer excreted from the body Ramani, Michigan State University

21 Carbon footprint reduction strategy using content Measuring 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/C-bioplastic + 6 O 2 6 CO2 + 6 H2O; DG 0 = -686 kcal/mol ANAEROBIC Glucose/C-bioplastic 2 lactate; ΔG 0 = -47 kcal/mol CO 2 + CH 4 CO 2 is the quantitative measure of the ability of the microrganisms present in the disposal environment to utilize/assimilate the test C-bioplastic, which is the sole C-source available for the microorganisms -- biodegradation/bioassimilation 20

22 Carbon footprint reduction strategy using content Measuring biodegradability % C conversion to CO2 (% biodegradation) lag phase biodegradation degree biodegradation phase plateau phase O 2 CO 2 Compost & Test Materials Time (days) 21

23 Carbon footprint reduction strategy using bio content Biodegradability under composting conditions Specification Standards ASTM D6400, D6868, D7021 Specification Standards EN (European Norm) Specification Standards ISO (International Standard) Biodegradability under marine conditions Specification Standard D 7021 Biodegradability Test Methods ASTM Standards Soil D5988 Anaerobic digestors D 5511, ISO Biogas energy plant Accelerated landfill D 5526 Guide to testing plastics that degrade in the environment by a combination of oxidation and biodegradation ASTM D 6954 Must provide results from the test methods could be zero or 50 or 100 percent --- generally not provided but claim of complete biodegradability made 22

24 Carbon footprint reduction strategy using bio content Problems with incomplete and partial biodegradation Thompson, R.C. et al Lost at sea: Where is all the plastic? Science 304, 838, 2004 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 From Algalita Marine Research Foundation 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. Takada et al Environ. Sci. Technol. 2001, 35, Blight, L.K. & A.E. Burger Occurrence of plastic particles in seabirds from the Eastern North Pacific. Mar. Poll. Bull. 34: Phil. Trans. Royal. Soc. (Biology) July 27, 2009;

25 Sorting through facts, hypes, claims (misleading) GREEN WASHING

26 Green Washing Claims -- Additive Technology Plastic products with our additives at 1% levels will fully biodegrade in 9 months to 5 years wherever they are disposed like composting, or landfills under both aerobic and anaerobic conditions The 50% Bio-Batch film did not degrade as completely or as quickly as the cellulose. At the end of the test, 19% of the film had degraded. The results of the aerobic degradation tests indicate that, in time, plastics produced using Bio-Batch pellets will biodegrade in aerobic conditions. DATA DOES NOT SUPPORT THE CONCLUSIONS!

27 MISLEADING BIODEGRADABILITY CLAIMS

28 MISLEADING CLAIMS UNSUPPORTED BY DATA Oxo-biodegradable polyethylene (PE) film claims The technology is based on a very small amount of prodegradant additive being introduced into the manufacturing process, thereby changing the behavior of the plastic and the rate at which it degrades. The plastic does not just fragment, but is then consumed by bacteria and fungi and therefore continues to degrade to nothing more than carbon dioxide, water and biomass with no toxic or harmful residues to soil, plants or macro-organisms Designed to interact with the microorganisms present in landfills, composters, and almost everywhere in nature including oceans, lakes, and forests. These microorganism metabolize the molecular structure of the plastic breaking it down into soil Combined with an oxo-biodegradable proprietary application method to produce films for bags. This product, when discarded in soil in the presence of microorganisms, moisture, and oxygen, biodegrades, decomposing into simple materials found in nature. Completely breakdown in a landfill environment in months leaving no residue or harmful toxins and have a shelf life of 2 years In each of the above cases scientific substantiation showing carbon conversion to CO2 using established standard test methods NOT PROVIDED

29 BIODEGRADABILITY CLAIMS Chem. Commun., 2002, (23), A hypothesis was developed, and successfully tested, to greatly increase the rates of biodegradation of polyolefins, by anchoring minute quantities of glucose, sucrose or lactose, onto functionalized polystyrene (polystyrene-co-maleic anhydride copolymer) and measuring their rates of biodegradation, which were found to be significantly improved PRESS Sugar turns plastics biodegradable. Bacteria make a meal of sweetened polythene and polystyrene. weight loss of only 2-12%, Only sugar is being assimilated, PE chain intact Is this a genuine example of biodegradable plastic?

30 Carbon Summary footprint reduction strategy using bio content To clearly communicate and articulate the environmental value proposition or attributes of biobased products and send a clear message, the reporting requirement are : material carbon footprint reductions using bio (carbon) content analysis (ASTM D6866) addresses the global warming potential impact category End-of-life options like biodegradability in a defined disposal environment (like composting, anaerobic digestion) using ASTM standards addresses several environmental impact categories LCA is a useful and important tool that helps define the environmental impact for the process of converting the bio or petro feedstock into product. However, it is a process carbon footprint, and has a number of constraints and issues. The fundamental driver or switch to biobased products is the material carbon footprint reductions arising from the short-term biogenic carbon cycle the rate and time scales of CO 2 sequestration is in balance with the use and release resulting in a carbon neutral footprint. In contrast to the long-term carbon cycle for petro/fossil feedstocks - the rate and time scale of CO 2 sequestration is in millions of years and the rate and time scales of use and release in a 10 year time frame End of Life issues -- Understand biodegradability and need to define disposal environment, time to complete biodegradation Beware of biodegradability claims verify with data 30