OCEAN PLASTICS - WordPress.com...8 million tons of plastic deposited into ocean annually - 10x increase by 2020 80% of marine debris estimated to be ocean plastics Marine life at risk

OCEAN PLASTICS

Marco, Alex, Mariana & Samhttps://www.projectaware.org/news/were-now-million-plastic-bottles-minute-91-which-are-not-recycled

● 8 million tons of plastic deposited into ocean annually - 10x increase by 2020

● 80% of marine debris estimated to be ocean plastics

● Marine life at risk● In 2015, only 9.1% of plastic was recycled

Ocean Plastics are a Serious Problem

Background Approach Inspiration Technical Performance Overview

Health Overview Strategies Conclusions

www.coastalseekers.com/story/reducing-plastic-pollution-in-our-oceans-world-environment-day/

● PET and PE together account for up to 30% of all plastics, with some of the most common applications being bottles and product containers

● Both show negligible marine degradation○ Micro and nano plastics

● Both have been shown to lead to high rates of sorption of POPs○ Large surface area

Current Plastics are Inadequate





● Goal: If plastics reach the ocean, they will break down in the environment in as little time as possible○ Breakdown products will not pose

hazards to the marine environment○ Products will not pose health hazards to

humans

https://www.pinterest.com/pin/60939401183116790/?lp=true

Approach: Reduce Impact of Method Products



Mechanical Thermal UV/Radical Hydrolytic Biological

Synthetic Polymer Degradation Processes



Modern plastics degrade slowly in nature

A large number of polymers degrade readily in the environment due to bacterial and fungal processes:

1. Cellulose (polysaccharides)2. Keratin (proteins)3. DNA (nucleic acids)

Our goal was to find polymers with these same properties- high durability but susceptible to enzymatic degradation- that also maintained thermoplastic properties

https://www.flickr.com/photos/jsjgeology/27105228293

https://da.wikipedia.org/wiki/Tr%C3%A6_(materiale)#/media/File:Egeved.JPG

https://en.wikipedia.org/wiki/File:DNA_Structure%2BKey%2BLabelled.pn_NoBB.png

Inspiration: Natural Polymers



Technical Performance



Technical Performance: Strategies

Biopolymers as Thermoplastic

Alternatives

Polymer Crystallinity and Biodegradation

Non- Thermoplastic

Alternatives

Biodegradation Enhancing Additives



ThermoplasticsThermoplastics soften when heated and harden when cooled. This allows them to be remolded and recycledAdvantages:

● Recyclable● Reshaping capabilities● Chemical resistant● Hard crystalline or rubbery surface

Thermoplastic Disadvantages:

● Expensive● Can melt if heated

Before After

https://commons.wikimedia.org/wiki/File:Plastic_bottle.jpg




Barrier PropertiesWater Permeability

Thermal Properties Glass transition and melting

temperatures

Tensile Properties Strength, elongation at break

Moisture and product dehydration

Resistance and flexibility

Polymer compatibility and stability




Polymer Barrier Properties Tensile Properties Thermal PropertiesH2O Permeability

(g mm/m2 day atm)Elongation at

break (%)Tensile

Strength (MPa) Tm (°C) Tg (°C)

PET 0.5-2 300 55 260 67-81PE 0.5-2 298 22-29 115–135 < -50



Environmental Performance- % Degradation

1. Standardized biodegradation (based on ASTM standards): 90% converted to CO2 after 180 days at 30°C in seawater with indigenous microbial culture

2. Abiotic degradation (chemical hydrolysis only): relevant to aquatic environments with diluted microorganism concentrations



Brannigan et. al. (2016)

Polylactic acid (PLA)

NatureWorks®-Cargill Dow (USA) and Galacid®-Galactic (Belgium)

● 10% of total biopolymer production capacities in 2013

● Made from renewable sources-100 % Bio-based content

● High transparency, high molecular weight, and good resistance to acids and oils

Biodegradable Polymers



http://www.worldcentric.org/biocompostables/cups/pla-cold-cups

https://commons.wikimedia.org/wiki/File:Polylactid_sceletal.svg

Environmental Performance● PLA will compost in industrial

facilities. Hydrolysis needs higher temperatures

● Degradation according to ASTM standards: 3.11% in 180 days

● Abiotic degradation 14% after 18 weeks

PLA Performance




Medium water barrier

Similar strength to PET

Low elongation at break, brittle

Tm and Tg similar to PE & PET


Polyhydroxyalkanoates (PHAs)Produced by the bacterial fermentation of sugars and lipids and are synthesised by a very wide range of microorganisms

Made up 1.6% of total biopolymer production capacities in 2013

PHBHx (Kaneka) and PHBO (Nodax by P&G) show greater biodegradation rates



https://en.wikipedia.org/wiki/Polyhydroxyalkanoates#/media/File:Poly-(R)-3-hydroxybutyrat.svg

PHA R

PHB -CH3

PHBV (BiopolTM) -CH3 and -CH2CH2CH3

PHBHx (Kaneka) -CH3 and -CH2CH2CH3

PHBO (Nodax) -CH3 and -(CH2)4CH3 Noda et. al. (2018)

Environmental Performance

PHBHx-Performance




Good water barrier

Similar strength to PE

Good elongation at break, ductile

Tm and Tg similar to PE & PET

Polymer Degradation according to ASTM standards

Abiotic degradation

PHA (Nodax) 45% in 180 days

PHB 89% in 43 days ~8.5% in 1 year

PHBHHx 88.1-89.4% loss 149 days at 30 °C


Polycaprolactone (PCL)

CAPA®- Solvay (Belgium), Tone®- Union Carbide (USA) or Celgreen®-Daicel (Japan)

● Non-renewable feedstock (fossil fuel based)

● Used in medical applications for long-term implants and controlled drug release applications

● Not widely used in packaging because of large costs

● Good chemical resistance to water, oil, solvent and chlorine



https://en.wikipedia.org/wiki/Polycaprolactone#/media/File:Polycaprolactone_structure.png

Environmental Performance● Degradation according to ASTM

standards 80% in 56 days at RT● Abiotic degradation <2% after 18

weeks● Slow hydrolytic degradation time

because of its hydrophobicity● PCL degrading microorganisms

were found in deep water (high pressure, low temperature)-these were not able to degrade PHAs or PLA

PCL Performance




Poor water barrier

Similar strength to PET

Low Tm Good elongation at break, ductile

Biopolymer BlendsBlends can improve:

1. Biodegradation

2. Material properties● PLA/PHA, PHA acts as

lubricant and plasticizer● PLA/PCL improved

mechanical properties, little degradation

3. Cost ● PCL +starch (plastic bags)

Sashiwa et. al. (2018)



Entry PHBHHx/PLA (wt/wt) Form Average Particle

Size (µm)

1 100/0 Powder 440 342 80/20 Powder 420 333 60/40 Powder 430 324 40/60 Powder 440 265 0/100 Powder 490 1

Amylose, Cellulose, or Starch:- improve degradation times by up to 70% with minimal changes to physical properties. -Polysaccharide believed to initiate bacterial growth, leading to co-polymer breakdown

Polymer Additives: Sacrificial PolymersConfounding issues:● Little data available in

biopolymers● Very few studies

available using similar metrics to those used in biopolymer comparisons

● Polymer dependent effects are hard to predict

https://upload.wikimedia.org/wikipedia/commons/5/52/219_Three_Important_Polysaccharides-01.jpg



Photosensitizing compounds:● Primarily Fe or Ca Stearate, Cu

Phthalocyanine-added at <1% level● Generate singlet oxygen- leads to radical breakdown

of polymer chains. ● Up to 95% decrease in Mw, 40% decrease in weight

Polymer Additives: PhotosensitizersConfounding issues:● Little data available in

biopolymers● Very few studies

available using similar metrics to those used in biopolymer comparisons

● Polymer dependent effects are hard to predict



Crystallinity & Polymer Degradation Processes

https://upload.wikimedia.org/wikipedia/commons/7/72/Amorphous_vs_Crystalline.jpg



Crystallinity & Polymer Degradation Processes

https://upload.wikimedia.org/wikipedia/commons/7/72/Amorphous_vs_Crystalline.jpg



Crystallinity & Polymer Degradation Processes● Lower crystallinity leads to faster

degradation● This holds true for many polymers● Relative impact is polymer dependent and

affected by polymer molecular weight● Decreasing crystallinity affects mechanical

properties- less brittle- less stable● Barrier properties altered with crystallinity,

particularly water and oxygen permeability● Maximum impact is 2% increase in

degradation per 1% change in crystallinity



Nature already contains attractive solutions for fluid containment

Fruits as Containers

https://www.flickr.com/photos/35832540@N03/3330701660

Coconuts represent a 2 part containment: cellulose exterior with a fatty/ waxy interior to hold fluid

Tomatoes use a thin hydrophobic barrier coupled with interior structures to contain fluid. Biological degradation rapidly eliminates

https://commons.wikimedia.org/wiki/File:Tomato-cut_vertical.png



Calcium Alginate:

Non-Thermoplastic Alternatives: Alginate

● Alginate is a linear polysaccharide extracted from brown algae

● Calcium reduces the solubility in water of alginate films, as well as their flexibility

● Modifying the Ca2+ counterion (eg. lactate) improves barrier properties

https://commons.wikimedia.org/wiki/File:Perles_d%27abricot_et_feuille_de_basilic.jpg



Composite packaging:

Non-Thermoplastic Alternatives: Composites

● Alternating layers of polymer, paper, and optional metal film

● Reduces polymer required by supplementing paper/cellulose

● Difficult to recycle due to combination of materials preventing separation

● Cellulose acts as a natural sacrificial polymer

https://de.wikipedia.org/wiki/Datei:TBA_packaging_components.gif#/media/File:TBA_packaging_components.svg



Alginate performance metrics:

Composite packaging performance metrics:

Performance of Non-Thermoplastic Alternatives

Barrier Properties H2O Permeability(g mm/m2 day atm) <12500

Tensile PropertiesElongation at break (%) 11.5Tensile Strength (MPa) 59.7Tensile Modulus (GPa) 0.6

Barrier Properties H2O PermeabilityDependent on polymer .5-300

Thermal Properties Tg(°C) 10-150



Poor water barrier

Good water barrier

Health Performance Overview



● Primary toxicological pathways1. Micro & nano plastic toxicity 2. POP exposure through plastic sorption 3. Direct toxicity in products

Health Performance Overview



Microplastic Exposure is a Threat

● 2 potential exposure routes:○ Directly in Method

products○ Marine organisms

→ trophic transfer

Lusher et al. 2017.



● Micro and nano plastics causes significant toxicological outcomes

Lusher et al. 2017.

Micro and Nano Plastics Health Impacts



Microplastics> 150 µm no absorption< 150 µm110 µm in portal vein

≤ 20 µm

Biological Level Polyethylene size Effect

Macromolecules 110nm - 30µm DNA damage, changes in gene and protein expression

Cells 300nm - 10µm Cell clotting, necrosis, apoptosis, oxidative stress

Tissues 600nm - 21µm Inflammation and bone osteosis

Exposure to POPs through microplastics in seafood constitutes a small proportion of total dietary intake of POPs

Smith et al. 2018.

Human Exposure to POPs through Microplastics



Compound Ratio Intake Microplastic/Total Dietary Intake (pg/kg bw/day) (%)

Non-dioxin like PCBs 0.03 - 0.007

DDT 0.1 - 0.02

PAHs 0.004 - 0.0000002

BPA 0.00002 - 0.000005

PBDEs 0.003 - 0.0007

Health Impacts of POPs

● Human health outcomes linked to POP exposure through micro/nano plastics is limited

● Chronic exposure is a concern○ Epigenetic alterations○ Neurobehavioral deficits ○ Altered insulin secretion

https://commons.wikimedia.org/wiki/File:DDT_chemical_structure_highres.png

DDT



● Exposure in Method products will typically be dermal

● Group 1 endpoints○ Chronic and/or life threatening endpoints○ Potentially induced at low doses○ Trans-generational potential

● Group 2 endpoints ○ Endpoints that can typically be mitigated

Direct Toxicity Health Exposure & Endpoints



Direct Toxicity Methodology

3 = Low Risk No (+) studies, no (+) modeling, or stated by AL2= Moderate Risk 1 (+) study or prediction, or stated by AL1 = High Risk 2+ (+) studies, or stated by AL

Unknown Following extensive review of the literature, no significant evidence could be found

Data Gap As labeled in GreenScreen or authoritative body

LegendPrimary Chemical

Breakdown Product

Additives/ contaminants

Monomer

Hazard tables for each chemical is generated

through literature review & toxicity modeling

ChemicalGroup I Human Endpoints Group II and Group II* Endpoints

Carcinogenicity/Mutagenicity

Developmental/Reproductive

Toxicity

Endocrine Activity Acute Toxicity Systemic

Toxicity (acute)Systemic Toxicity

(C)Neurotoxicity

(A)Neurotoxicity

(C)Skin, Eye, Respiratory

Irritation (A)

Existing ChemicalsPET 2, L U 2, L 3, L U U U U 2, LEthylene glycol 3, H 1, H 3, L 2, H 1, H 1, H 1, H 3, H 2, HTerephthalic acid 2, L 2, H 2, L 3, H 2, H 1, H 2, H 3, H 2, HPhthalic acid 2, L 2, L 3, L 2, L 2, L U U U 1, LPolyethylene (PE) 1, L U U 3, M U 3, M U U 2, HEthylene 2, H 3, L 3, L 2, L 2, L U 2, L 1, L 2, L



Direct Toxicity Methodology cont. ● Final evaluation, based on Faludi et al. (2016)

○ Weighted average across monomers & polymers ○ Averages & Ranges → worst case & best case ○ Limitations & Assumptions

■ Weights ■ Unknowns & data gaps → scoring ■ Successful evaluation of the literature ■ Scores impacted by # monomers/breakdown products included■ Toxicity of monomers/breakdown as significant as parent compound

Note that numerically low scores indicate a higher hazard

Carc/Mut Dev/Repro/ED Acute ST/N/Ir Chronic ST/N Overall Hazard ScorePET range 2-3 (1 U) 1-3 (1 U) 1-3 (3 U) 1-3 (3 U) 1.26-3PET average 2.25 2.14 1.92 2.2 2.14weighting coefficient 0.2625 0.2625 0.2125 0.2625



Direct Toxicity Methodology cont. ● Graphs represent the weighted

range and weighted average of the hazard score for each chemical

Note that numerically low scores indicate a higher hazard



Chemical Overall Hazard Score Range

Existing ChemicalsPET 1.26-3 2.14PE 1.74-2.74 2.17

Guiding principles:● If a compound is good at

concentrating Persistent Organics (POPs) but has a short lifetime, it can still be a good option

● Absolute data is rare, hard to assign confidence rating

● Hydrophobicity has non direct correlation to sorption rate

Risk Assessment Degradation time Sorption of POPs

Low Risk <6 months with some hydrolytic <50 ug/g polymer

Moderate Risk 6 months to 1 year 50 to 300 ug/g polymerHigh Risk > 1 year >300 ug/g polymer


Data Gap As labeled in GreenScreen or other authoritative body

Environmental Performance: Methodology



Guiding principles:● If a compound is good at

concentrating Persistent Organics (POPs) but has a short lifetime, it can still be a good option

● Absolute data is rare, hard to assign confidence rating

● Hydrophobicity has non direct correlation to sorption rate

Risk Assessment Degradation time Sorption of POPs

Low Risk <6 months with some hydrolytic <50 ug/g polymer

Moderate Risk 6 months to 1 year 50 to 300 ug/g polymerHigh Risk > 1 year >300 ug/g polymer


Data Gap As labeled in GreenScreen or other authoritative body

Environmental Performance: Methodology



Existing Chemicals Particle Degradation Sorption of POPsPolyethylene terephthalate(PET) High Risk Low Risk

Polyethylene(PE) High Risk Moderate Risk

Strategy #1



Strategy 1: Bio-polymers● Our goal is to provide a potential solution with limited health effects

that exhibit fast degradation times and promising mechanical properties

● PCL and PHAs (PHBHx) exhibit fast degradation times in seawater systems with microbial cultures present

● PHBHx has the best barrier and tensile properties among the biopolymers




Overall Score Average

Particle Degradation

Sorption of POPs Barrier Tensile

PropertiesPHA 2.05-2.79 2.55 Low Risk Moderate GoodPHBHx 2.05-2.78 2.59 Low Risk High Risk Good GoodPLA 2.56-2.99 2.81 High Risk Low Risk Moderate ModeratePCL 2.31-2.99 2.71 Moderate Risk High Risk Poor Moderate

Strategy 1: Bio-polymers






Sorption of POPs

PET 1.26-3 2.14 High Risk Low RiskPE 1.74-2.74 2.17 High Risk




Sorption of POPs Barrier Tensile

PropertiesPHA 2.05-2.79 2.55 Low Risk Moderate GoodPHBHx 2.05-2.78 2.59 Low Risk High Risk Good GoodPLA 2.56-2.99 2.81 High Risk Low Risk Moderate ModeratePCL 2.31-2.99 2.71 Moderate Risk High Risk Poor Moderate

Strategy #2



Strategy 2: Additives

Chemical Overall Hazard Score RangeO Particle

DegradationSorption of

POPsIron stearate 2.00-2.21 2.21 Low RiskCopper phthalocyanine 3 3 Low RiskCellulose 2.00-3.00 2.5 Low Risk

● UV sensitizers decrease the time required to take plastics below the 10,000 MW cutoff for efficient biodegradation

● Relatively low concentration (<1% by mass) and low toxicity make for promising alternatives

● Sacrificial polysaccharides can be added with minimal decreases in performance while promoting bacterial growth and breakdown



Strategy 2: Additives

Chemical Overall Hazard Score RangeO Particle


POPsIron stearate 2.00-2.21 2.21 Low RiskCopper phthalocyanine 3 3 Low RiskCellulose 2.00-3.00 2.5 Low Risk






Sorption of POPs

PET 1.26-3 2.14 High Risk Low RiskPE 1.74-2.74 2.17 High Risk Risk

Strategy #3



Strategy 3: Non-Thermoplastics

Non- Thermoplastic Alternatives

● Non-thermoplastics provide an attractive model that breaks from traditional packaging styles

● Composite packaging utilizes all of the methodologies from thermoplastics to ensure the hydrophobic layer degrades rapidly

● Alginate packaging is as a fun new direction for consumers and represents the most attractive solution in terms of degradation rate and potential health impact






Alginate 2.00-3.00 2.57 Low RiskCalcium lactate 1.73-2.74 2.46 Low Risk

Strategy 3: Non-Thermoplastics

Non- Thermoplastic Alternatives






Alginate 2.00-3.00 2.57 Low RiskCalcium lactate 1.73-2.74 2.46 Low Risk




PET 1.26-3 2.14 High RiskPE 1.74-2.74 2.17 High Risk

Strategy #4



Strategy 4: Combinatorial Strategy

Crystallinity

● Each of the three strategies could be used in combination to fine tune polymer properties

● This solution represents a new set of dials to adjust when designing new packaging

AdditivesBiopolymers

+ +



Conclusion



Health/Technical Performance EvaluationChemical Health Hazard

RangeHealth Hazard

AverageParticle


POPsExisting Chemicals

PET 1.26-3 2.14 High Risk Low RiskPE 1.74-2.74 2.17 High Risk Moderate Risk

Alternative BiopolymersPHAs 2.05-2.79 2.55 Low RiskPHBHx 2.05-2.78 2.59 Low Risk High RiskPLA 2.56-2.99 2.81 High Risk Low RiskPCL 2.31-2.99 2.71 Moderate Risk High Risk

Alternative Non-thermoplasticsAlginate 2.00-3.00 2.57 Low RiskCalcium lactate 1.73-2.74 2.46 Low Risk

Alternative AdditivesIron stearate 2.00-2.21 2.11 Low RiskCopper Phthalocyanine 3 3 Low RiskCellulose 2.00-3.00 2.5 Low Risk



Direct Toxicity of Current Chemicals & Alternatives



Existing Chemicals Particle Size

PET Moderate Risk

PE

Alternate Chemicals

PHAs Low Risk

PHBH

PLA

PCL

Alginate Low Risk

Cellulose Low Risk

Alternatives’ Improvements

● Improves on technical/environmental performance by:1. Fast degradation leading to little accumulation2. Bypassing recycling barrier by making everything degradable/

compostable3. Renewable feedstocks available for most polymers

● Improve on health safety by:1. Decreasing direct toxicity compared to PE and PET2. Decreasing nano, micro & macroplastic exposure3. Potential decrease in POP exposure due to increased degradation time



● Further steps:○ Evaluate impact of combinatorial solutions ○ Photo-oxidants must be evaluated to determine

impact on aquatic degradation of biopolymers○ Health & environment impacts of biopolymer

production ● Scale of marine plastics● Understand link between human health outcomes

and bioaccumulation

Future Directions



ANY QUESTIONS?https://www.projectaware.org/news/were-now-million-plastic-bottles-minute-91-which-are-not-recycled

Special Thanks to:Kaj JohnsonMichelle ByleRyan Williams

Meg SchwarzmanDavid FaulknerBilly Hart-CooperTom McKeag

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OCEAN PLASTICS - WordPress.com...8 million tons of plastic deposited into ocean annually - 10x increase by 2020 80% of marine debris estimated to be ocean plastics Marine life at risk