Biotechnology for preventing environmental contamination … · 2018-08-02 · Narayan Biotechnology for preventing environmental contamination (current and future trends and issues)

Narayan

September 17, 2010

Ramani Narayan

University Distinguished Professor

[email protected]

Biotechnology for preventing environmental

contamination (current and future trends and issues)

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

Copyright Ramani Narayan

Presentation at OECD Workshop on

Environmental Biotechnology, Rimini, Italy

Narayan

Biotechnology for preventing environmental

contamination (current and future trends and issues)

• Using bio renewable carbon feedstock to manufacture chemicals, plastics (& fuels)

• Reducing carbon footprint (Global warming/climate change issues)

• End-of-life

• Organics Recovery Strategy

• Biodegradability in industrial composting disposal systems

• Biodegradability in anaerobic digestors (for energy recovery)

• Environmental Safety

• Release into soil environment – soil biodegradability

• Waste water treatment system – anaerobic biodegradability

• Release into oceans – marine biodegradability

Narayan

Switching the “petro/fossil” CARBON to “bio-renewable”

Carbon reduces the carbon footprint:

• Reducing heat trapping CO2 emissions -- Minimizing global

warming/climate change problems

• Global warming potential (GWP – LCA terminology)

• Using (renewable) biomass feedstock as opposed to

petro/fossil feedstock – energy/environmental security

• Economic development – empowering rural farm, forestry and

allied manufacturing industry

Carbon footprint reduction strategy using bio content

Value Proposition for Biobased (Biomass/Renewable) Products (chemicals, & plastics)

3

Narayan

Carbon footprint reduction strategy using bio content Value Proposition for bio carbon vs petro/fossil carbon

4

CO2 + H2O (CH2O)X + O2photosynthesis

sunlight energy

Biomass, Ag & Forestry crops &

residues

NEW CARBON

Fossil Resources (Oil, Coal, Natural gas) -- OLD CARBON

> 106 YEARS USE – for materials,

chemicals and fuels

Rate and time scales of CO2 utilization is in balance using bio/renewable feedstocks

(1-10 years) as opposed to using fossil feedstocks

1-10 years

1-10 years

MATERIAL CARBON FOOTPRINT

Short (in balance) sustainable carbon cycle using bio renewable carbon feedstock

Ramani Narayan, Michigan State University

CARBON FOOTPRINT BASICS – Value Proposition

C

O

O CH2 CH2 OC

On

PET

Bio/renewable

feedstock

Crops & residues

(e.g. Corn, soybean

sugarcane)

Tree plantations

Lignocellulosics

Algal biomass

Oil, Coal,

Natural gas

H2C CH2

nPE

Naptha Ethylene

POLYETHYLENE

Ethylene oxide Ethylene

Glycol

POLYESTERS

MATERIAL CARBON FOOTPRINT PROCESS CARBON FOOTPRINT

EtOH

BIO monomers

Sugars, Oils

CH

CH3

C

O

O

PLAn

PLA, PHA’s

polyurethanes;

polyamides (Nylons);

polyesters


What is the impact of the material/product’s carbon footprint on the

environment ? –

100 Kg of polyethylene will result in net ?? Kg of CO2 released into

the atmosphere

Based on “petro carbon” vs “bio carbon”

100 Kg of polyester (PET )acid will results in net ?? Kg CO2 release

into the atmosphere

based on how many “petro carbons” vs “bio carbons”

Carbon footprint reduction strategy using bio content Material Carbon Footprint

6

C

O

O CH2 CH2 OC

On

PET

H2C CH2

nPE


314 kg of CO2 emissions reduction for every 100 kg of PE

resin in which the petro carbon is replaced with bio carbon

Material Carbon Footprint

0

50

100

150

200

250

300

350

PE/PP PET Bio-PE/PET/PLA

Kg of CO2 per 100 Kg resin

ZERO CARBON

FOOTPRINT

314 kg of CO2 emissions reduction for every 100 kg of PE

resin in which the petro carbon is replaced with bio carbon


PLASTICS LANDFILLED NO CO2 RELEASE -- SCENARIO

Material Carbon Footprint

Kg of CO2 per 100 kg of resin

-320

-270

-220

-170

-120

-70

-20

30

80

1 2

Zero footprint -- product

recycled, no release of

gas to the environment

PE/PP BIO-PE

Narayan


Measurement of bio (carbon) content – the Principle

9

C-14 signature forms the basis of

Standard test method to quantify

biobased content (ASTM D6866)

12CO2

Biomass/Bio-organics

Fossil Resources

(petroleum, natural gas, coal)

> 106 years

14CO2 – Solar radiation

(12CH2O)x (14CH2O)x

(12CH2)n (12CHO)x

NEW CARBON

OLD CARBON

Narayan, ACS (an American Chemical Society publication) Symposium Ser.939,

Chapter 18, pg 282, 2006

14N 14C 14CO2

Cosmic

radiation

12CO2

Narayan

Carbon footprint reduction strategy using bio content Measurement of biobased (carbon) content – ASTM D6866

10

C-product combusted to CO2

14C/12C ratio is compared directly with a oxalic acid radiocarbon

standard reference material (SRM 4990c) that is 100% new (bio)

carbon.

13.56 dpm/g is the absolute value of the primary oxalic acid standard

(SRM 4990b) corresponding to 100% biobased carbon content.

To correct for the post 1950 14C injection into the atmosphere, all

pMC values (after correction for isotopic fractionation) must be

multiplied by 0.93 to better reflect the true biobased carbon content

of the sample.

Contains concentration of 1.2 x 10-12 % of C-14 isotope equivalent to

100% bio carbon content

Narayan

Calculations -- Example

C

O

O CH2 CH2 OC

On

PET

1. Given the PET structure above, what would the percent biobased (renewable)

carbon content (EG component – O-CH2-CH2-O- is from biomass feedstock) [20%]

2. How much Kg of biomass carbon is present in 100 Kg of bio-PET (EG component –

O-CH2-CH2-O- is from biomass feedstock) [12.5 Kg]

3. How much CO2 reductions achieved by incorporating biomass derived EG in to

37.5 million metric tons of PET [17.19 million metric tons]

4. The above CO2 emissions reduction eliminates consuming how many million

barrels of oil each year [40 million barrels of oil]

5. If the above sample was subject to ASTM D6866 analysis, what biobased

(renewable) carbon content would be obtained [20% biboased content]

ASSIGNMENT PLANTBOTTLE

BIO

Narayan

Carbon footprint reduction strategy using bio content Terminology:

12

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

ASTM D6866 – Standard Test Methods for Determining the Biobased Content of

Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis

Narayan

Take Home Message

– Use bio (carbon) content analysis (ASTM D6866) to

document verifiable CO2 reductions

– Intrinsic “material carbon footprint” reductions provides

the rationale for switching from a petro/fossil carbon

feedstock to a bio-renewable carbon feedstock

– Remember – LCA methodology provides the process carbon and

environmental footprint not material carbon replacement

footprint

– Process carbon footprint – impact of GHG emissions from the

various process step to convert the feedstock to final product

and ultimate disposal (cradle to grave)

Narayan

Carbon footprint reduction strategy using bio content Process Carbon Footprint – the LCA trap

14

Carbon Footprint Including Conversion

0

100

200

300

400

500

600

700

Starch/PLA PET PP (85.71%c)

CO2 released during coversion feedstock CO2 release

Narayan

Carbon footprint reduction strategy using bio content Biodegradability – A misused and abused term

15

Using biodegradability as an end-of-life strategy to completely remove

single use short life disposable products or chemicals from the

environmental compartment in a safe and efficacious manner via

microbial assimilation (microbial food chain)

Must provide information (using ASTM. EN, ISO Standards)

• Disposal environment (like composting, anaerobic digestor,

marine, soil or landfill??

• Time to complete biodegradation

• Degradable, partial biodegradable not acceptable – serious

health and environmental consequences

• Phil. Trans. Royal. Soc. (Biology) July 27, 2009; 364

Narayan

Carbon footprint reduction strategy using bio content Measuring biodegradability

16

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

Glucose/C-bioplastic + 6 O2 6 CO2 + 6 H2O; DG0’ = -686 kcal/mol

AEROBIC

ANAEROBIC

Glucose/C-bioplastic 2 lactate; DG0’ = -47 kcal/mol

CO2 + CH4

CO2 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

Narayan

Carbon footprint reduction strategy using bio content Measuring biodegradability

17

0

10

20

30

40

50

60

70

80

90

100

0 20 40 60 80 100 120 140 160 180 200

Time (days)

% C

c

on

ve

rsio

n to

C

O2 (%

b

io

deg

ra

da

tio

n)

lag

phase

biodegradation phase

plateau phase

biodegradation degree

O2

Compost

& Test

Materials

CO2

Narayan


18

Biodegradability under composting conditions

• Specification Standards ASTM D6400, D6868, D7021

• Specification Standards EN 13432 (European Norm)

• Specification Standards ISO 17088 (International Standard)

Biodegradability under marine conditions

• Specification Standard D 7021

Biodegradability Test Methods – ASTM Standards

• Soil D5988

• Anaerobic digestors D 5511, ISO 15985

• 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

Narayan

OECD BIODEGRADABILITY TESTS FOR CHEMICALS

Ready biodegradability

– “if a chemical meets the “ready biodegradability” standard (OECD 301-B) then it is

assumed that the chemical will undergo rapid and ultimate biodegradation in most

environments including biological STP’s and that in such cases, no further

investigation of (bio) degradability of the chemical, or of the possible environmental

effects of transformation products is normally required”.

Pass criteria 60% theoretical carbondioxide (ThCO2) (TG 301 B) to be reached in

a 10-day window within the 28-day period of the test - US EPA

Inherent biodegradability

– tests of inherent biodegradability have been designed to assess whether the

chemical has any potential for biodegradation under aerobic conditions.

– Biodegradation above 20% of theoretical (measured as BOD, DOC removal or COD)

may be regarded as evidence of inherent, primary biodegradability

Ultimate biodegradability

– test compound is totally utilized, 100% biodegraded by microorganisms resulting in

the production of carbon dioxide, water, mineral salts, and new microbial cellular

constituents (biomass).

Inherent biodegradability term usage is problematic and misused

especially as it applies to products

Includes:

Definition, content verification, ASTM D6866

Biodegradability using ASTM D6400 and D6868 (paper coatings)

D7021 (marine)

performance requirements; and

assurance that products are available

U.S. Farm Security and Rural Investment Act of 2002 (P. L. 107-

171), Title IX Energy, Section 9002

FARM BILL

Federal Procurement of Biobased Products – the “biopreferred program” (www.biopreferred.gov)

• develop guidelines for designating biobased products

• publish a list & issue criteria for a designated biobased products list (DBL)

for federal purchase;

• “USDA Certified Biobased Product” labeling program

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

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

BIO PRODUCT TECHNOLOGY EXEMPLARS

DuPont’s 1,3-PDO ---- polyesters (Sorona) & renewably sourced products like Hytrel thermoplastic elastomers, Cerenol polymers

NatureWorks –40,000 t (300 MM lbs) PLA

PURAC – Lactic, lactide, Thailand (100,000 t)

BASF – 14, 000 t biodegradable polyesters – biobased polyesters incorporating PLA; 60,000 t plant 2010)

Novamont -- Bioresins

Natur-Tec -- Bioresins

Braskem (150 MM lbs), DOW (250 MM lbs)

Solvay – 60, 000 tons ethylene, 110, 000 t EtOH PVC

ADM-Metabolix – Polyhydroxyalkanoates (PHA’s)

Arkema – Polyamide 11 – high performance polymers

Biopolyurethanes – Ford, Toyota

Biofiber composites – auto components

BioPET --- Coca Cola’s plant bottle

Several others


DISCUSSION SLIDES

Narayan

Carbon footprint reduction strategy using bio content Problems with incomplete and partial biodegradation

23

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 – 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.

• Takada et al Environ. Sci. Technol. 2001, 35, 318-324

• Blight, L.K. & A.E. Burger. 1997. Occurrence of plastic particles in seabirds from the Eastern North Pacific. Mar. Poll. Bull. 34:323-325

• Phil. Trans. Royal. Soc. (Biology) July 27, 2009; 364

Thompson, R.C. et al. 2004. Lost at sea: Where is all the plastic? Science 304,

838, 2004

Narayan

Sorting through facts, hypes, claims (misleading)

GREEN WASHING

Narayan

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!

Narayan

MISLEADING BIODEGRADABILITY CLAIMS

Narayan

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 12-24 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

Narayan

BIODEGRADABILITY CLAIMS

Chem. Commun., 2002, (23), 2884 - 2885 – 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?

Documents

Biotechnology for preventing environmental contamination … · 2018-08-02 · Narayan Biotechnology for preventing environmental contamination (current and future trends and issues)