Types of intrinsic hazards...Chemicals in the Environment • Toxics Release Inventory (TRI) • 4.44 billion lbs. of toxic chemicals were released directly to air, water, and land

Green Chemistry:

Environmental and health protection

through innovation

Paul T. Anastas

Yale University

1

So.

All we have is…

energy

matter

energy

2010, Bloomberg News

Wegmans stops selling reusable bags after lead tests

2010, Bloomberg News

Wegmans stops selling reusable bags after lead tests

2010, NY Times

Hydrocarbons in Cereal

Stoke New Debate Over

Food Safety

2010, The Sun Chronicle

Toxic Beauty

2010, Maine Public Broadcasting Network

Report: Cosmetic Products Contain High Levels of Toxic

Chemicals

2009, BBC News

Deet bug repellent

'toxic worry'

2009, The

Charleston

Gazette

Study finds food-

wrapper

chemicals in

blood

Persistence

Chemicals in the Environment

• Toxics Release Inventory (TRI)

• 4.44 billion lbs. of toxic chemicals were released directly

to air, water, and land in 2011

– Only 650 of toxic chemicals and toxic chemical

categories out of 78,000 in commerce are tracked by

TRI

Absurdity then.

Absurdity now.

- Developmental

delays

- Infertility

- Cancer

- Obesity

- Behavioral

problems

Mahoney et al. Toxicol and applied Pharmacol,

2010.

Soto et al. Nature Reviews: Endocrinology, 2010.

Today.

Today.

Today.

Today.

70% of Smallmouth

Bass in the

Mississippi River

are intersex.

Source, USGS: http://www.usgs.gov/newsroom/article.asp?ID=2305

Today.

Over 90% of Florida

Panthers’ sperm are

abnormal. Many are

completely sterile.

And source Facemire et al.EHP, 1995.

Today.

Source : UNEP

The total volume of water on Earth:

~1.4 billion km3

Percent of total that is freshwater:

2.5%

Percent of Freshwater locked up in

ice & snow: ~70 %

Percent freshwater that is

drinkable: <1%

Today.

In developing countries, 70% of industrial wastes are dumped

untreated into waters where they pollute the usable water

supply. Source: UNEP

Today.

--Source, US EPA

In 2010, the U.S.

generated 30

million tons of

plastic waste.

Equal to the weight of

nearly 100 Empire

State Buildings.

Only 7 % was recovered for recycling.

Today.

The Pacific Trash Vortex Today.

Marine trash kills more than 1

million seabirds and 100,000

mammals and sea turtles each

year.

Source, UN

Statement

Today.

Montcoal Mine, West Virigina

April 2011

Death Toll: 29

Deepwater Horizon, Gulf of

Mexico

April, 2010

Death Toll: 11

Fukushima

Nuclear

Disaster,

Japan

March 2011

Toll?

Today.

• Doing the right things, wrong.

water

toxics climate energy

biodiversity

Unintended Consequences

Biofuels that

compete with

food, feed,

and land use

Unintended Consequences

Purifying

water with

acutely lethal

substances

Unintended Consequences

Renewable

energy through

the use of

precious, rare,

toxic metals in

photovoltaics

Unintended Consequences

Agricultural crop

efficiency from

persistent

pesticides

Unintended Consequences

Energy saving

compact fluorescent

light bulbs reliant on

toxic metals

How did we get there?

• Urgent and necessary challenges

• Noble goals

• Exciting science and technology

• Best of intentions

• Lack of systems thinking.

Design for a Systems Context

Awareness

Problems cannot be

solved at the same level

of awareness that created

them. A. Einstein

Definition

• GREEN CHEMISTRY:

The design of chemical products and

processes that reduce or eliminate the use

and generation of hazardous substances

Principles of Green Chemistry 1. It is better to prevent waste that to treat or clean up waste after it is formed.

2. Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.

3. Wherever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment.

4. Chemical products should be designed to preserve efficacy of function while reducing toxicity.

5. The use of auxiliary substances (e.g. solvents, separation agents, etc.) Should be made unnecessary wherever possible and, innocuous when used.

6. Energy requirements should be recognized for their environmental and economic impacts and should be minimized. Synthetic methods should be conducted at ambient temperature and pressure.

7. A raw material of feedstock should be renewable rather than depleting wherever technically and economically practicable.

8. Reduce derivatives - Unnecessary derivatization (blocking group, protection/ deprotection, temporary modification) should be avoided whenever possible.

9. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.

10. Chemical products should be designed so that at the end of their function they do not persist in the environment and break down into innocuous degradation products.

11. Analytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.

12. Substances and the form of a substance used in a chemical process should be chosen to minimize potential for chemical accidents, including releases, explosions, and fires.

Twelve Principles…Isn’t that how it

is done now?

• Entire industries are geared toward cleaning up after wasteful

chemical syntheses.

• Feedstocks are seldom selected with regard to hazard.

• Industrial chemicals products do not have minimal hazard as a

performance criterion

• Persistence of chemicals in the biosphere and in our bodies is a

major global health issue. (CDC 250 chemicals since 1945)

• The vast majority of organic chemicals are made by depleting (non-

renewable) feedstocks

• Our chemical industry deals with safety through engineering and

security through barricades.

Green Chemistry Design Framework Across the life-cycle

Waste Prevention

Atom Economy

Design For

Degradation

Less Hazardous

Reagents

Renewable Feedstocks

Design for Safety and Security

Green Analytical

Methods

Benign Solvent Systems

Use of Catalysis

Benign Product Design

Unnecessary

Derivatives

Energy Considerations

Origins

Of Materials Manufacturing Distribution Use End of Life

Journals

Articles

1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

Headlines

Research

Conferences

Networks

Business?

Green Chemistry across

Industrial Sectors

• Defense and aerospace – Adhesives, coatings, corrosion

inhibitors

• Automotive – Solvents, polymers, fuels

• Household cleaners – Surfactants, fragrances, dyes

• Cosmetics – Builders, chelating agents, dyes

• Agriculture – Pesticides, fungicides, fertilizers

• Electronics – Solder, housings, displays

• Pharmaceuticals

AqueousSolvents

Biobased

Transformations

Biobased materials

Alternative Energy Science

Synthetic Methodologies

Next Generation

Catalysts

Molecular

Self-Assembly

Breakthroughs

Green Nano

RT Ionic Liquids

Degradable Polymers

Biofuels Reactor Design

Super-

critical

fluids

We know what carbon dioxide

as waste looks like.

Emissions of Carbon

Increases in Carbon Dioxide

Global Change

CO2 for Extraction (Coffee)

CO2 as a Cleaner

CO2 in Concrete

• Materials Tech - Supramics

• CO2 Solutions

• Calera

• Carbon Sense Solutions

• Drexel University

• McGill University

• MIT

CO2 and the Integrated Biorefinery Alternative technologies for extraction, transformation, isolation and purification of value-added chemicals and fuels.

Algae-to-fuel and algae-to-chemical technologies Soh, L.; Zimmerman, J., Biodiesel Production Potential of Algal

Lipids Extracted with Supercritical Carbon Dioxide. Green Chemistry 2011, 13 (6), 1422-1429. Brentner, L. B.; Eckelman, M. J.; Zimmerman, J. B., Combinatorial life cycle assessment to inform process design of industrial production of algal biodiesel. Environmental Science & Technology 2011, 45, 7060-7067. Foley, P. M.; Beach, E. S.; Zimmerman, J. B., Algae as a source of renewable chemicals: opportunities and challenges. Green Chemistry 2011, 13, 1399-1405.

Solvents • Highest Volume Chemicals

• Amongst the Most Regulated Chemicals

• Widely distributed in the Environment

• High chronic and Acute Toxicity

• Significant Strat. Ozone Depleters

• Significant Atmosph. Ozone Generators

• Potent Green House Gas Potential

A PRIME OPPORTUNITY FOR GREEN

CHEMISTRY INNOVATION

Room Temperature Ionic Liquids

• Virtually no vapor pressure

• Tailored for performance

• BASF

– The BASIL Process

Bio-Based Solvents

• Gamma Valero Lactone

• Ligno-cellulosic derived

• Equal or superior performance to

classic organic solvents

15-20% of the total economy

80% of chemical products

90% of new chemical processes

Catalysis is

involved in:

VCI,

Positionspapier Katalyse, 2002

Serenade®: An Effective,

Environmentally Friendly Biofungicide

• Non-toxic alternative to traditional chemical pesticides and is compatible with organic and conventional farming

• Feedstock includes agricultural materials (soybeans, starches, sugars) from plant-based sources, reducing petroleum-based feedstocks; fermentation products are non-hazardous

• No synthetic chemical residues; non-toxic to beneficial insects and organisms and does not cause secondary disease or insect problems

• Safe toxicology profile allows for a 4 hour re-entry period for workers and a zero day pre-harvest interval

AgraQuest, Inc.

Voutchkova-Kostal, A. M.; Kostal, J.; Connors, K. A.; Brooks, B. W.; Anastas, P. T.; Zimmerman, J. B., Towards rational molecular design for reduced chronic aquatic toxicity. Green Chemistry 2012, 14 (4), 1001-1008. Voutchkova, A. M.; Kostal, J.; Steinfeld, J. B.; Emerson, J. W.; Brooks, B. W.; Anastas, P. T.; Zimmerman, J. B., Towards rational molecular design: derivation of property guidelines for reduced acute aquatic toxicity. Green Chemistry 2011, 13, 2373-2379. Voutchkova, A. M.; Osimitz, T. G.; Anastas, P. T., Toward a Comprehensive Molecular Design Framework for Reduced Hazard. Chem. Rev. 2010, 110, 5845-5882. Voutchkova, A. M.; Ferris, L. A.; Zimmerman, J. B.; Anastas, P. T., Toward Molecular Design for Hazard Reduction-Fundamental Relationships between Chemical Properties and Toxicity. Tetrahedron 2010, 66, 1031-1039.

Molecular Design for Reduced Hazard

Developing World Green

Chemistry

Developing countries are emerging as major markets and

sources of innovation for industrial biotech. Braskem, a

Brazilian chemicals firm, has commercialised

polyethylene—a commonly used plastic resin—made from

sugarcane. It is now working with Novozymes, a

pioneering Danish biotech firm, to repeat the trick for

polypropylene, another common plastic. And Brazil's

ethanol industry, already the world's biggest, wants to

move from first-generation ethanol (made from sugarcane)

to the next-generation cellulosic variety.

Biotechnology

Chemistry goes green

Biopolymer Sorbents for Arsenic

Removal

Yamani, J. S.; Miller, S. M.; Spaulding, M. L.; Zimmerman,

J. B., Enhanced arsenic removal using mixed metal oxide

impregnated chitosan beads. Water Research 2012, 46

(14), 4427-4434.

Miller, S. M.; Spaulding, M. L.; Zimmerman, J. B.,

Optimization of capacity and kinetics for a novel bio-based

arsenic sorbent,TiO2-impregnated chitosan bead. Water

Research 2011, 45 (17), 5745-5754.

Miller, Sarah M.; Zimmerman, Julie B., Novel, bio-based,

photoactive arsenic sorbent: TiO2-impregnated chitosan

bead. Water Research 2010, 44, 5722-5729.

Developing new catalysts and

methods for controlled

transformation of lignin and

lignocellulosic materials.

Catalytic transformation of lignocellulose Hansen, T. S.; Barta, K.; Anastas, P. T.; Ford, P. C.; Riisager, A., One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol. Green Chemistry 2012, 14, 2457-2461 . Matson, T. D.; Barta, K.; Iretskii, A. V.; Ford, P. C., One-Pot

Catalytic Conversion of Cellulose and of Woody Biomass

Solids to Liquid Fuels. Journal of the American Chemical

Society 2011, 133, 14090-14097.

Renewable Specialty

Chemicals

• Based on Green

Chemistry Principles

• Bio-based oils,

sugars, starches,

and oxygen.

• Flavors, fragrances,

and suractants

Is it really all we have?

energy

matter

energy

So.