Green Chemistry: Sustaining a High Technology Civilization

Terry CollinsLibrarian Watch: Introduction to New Hot Areas of Chemistry

ACS National Meeting, New Orleans—March 23, 2003

Green Chemistry: Sustaining a High Technology Civilization

Terry CollinsLibrarian Watch: Introduction to New Hot Areas of Chemistry

ACS National Meeting, New Orleans—March 23, 2003

A Sustainable CivilizationA Sustainable Civilization

• The daily activities of the people who comprise the civilization can be carried on into the indefinite future,

• without undermining the ability of future generations to live with at least a comparably advantageous welfare.

• The daily activities of the people who comprise the civilization can be carried on into the indefinite future,

• without undermining the ability of future generations to live with at least a comparably advantageous welfare.

“Altered Nature of Human Action”“Altered Nature of Human Action”

“All previous ethics…[have been based upon the premises]…that the human condition, determined by the nature of man and the nature of things,was given once for all; that the human good on that basis was readily determinable; and that the range of human action and therefore responsibility was narrowly

circumscribed. …[But] with certain development of our powers the nature of human action has changed, and…

[given rise to]… a whole new dimension of ethical relevance for which there is no precedent in the

standards and canons of traditional ethics.”The Imperative of Responsibility: Finding an Ethics for the Technological Age, Hans Jonas, U. Chic. Press, 1984

Economic Opportunity

Economic Opportunity

Interdisciplinary Research

Interdisciplinary Research

Educational Sea Change Educational Sea Change

Chemistry LeadershipChemistry Leadership

Ecospherical Responsibility of ChemistsEcospherical Responsibility of Chemists

Matter flows from ecosphere into human economy

Matter flows from ecosphere into human economy

Spent matter flows out of human economy toecosphere

Spent matter flows out of human economy toecosphere

Based on ideas of Herman DalyBased on ideas of Herman Daly

HumanEconomyHuman

Economy

ThemesThemes

SustainabilityEthics

Hans Jonas

SustainabilityEthics

Hans Jonas

Green Chemistry Principles

Anastas & Warner

Green Chemistry Principles

Anastas & Warner

Historyof the Ungreen

Markowitz & Rosner

Historyof the Ungreen

Markowitz & Rosner

GreenAccomplishments

PGCCAs

GreenAccomplishments

PGCCAs

Toxicology & Ecotoxicology

Bernd Jastorff

Toxicology & Ecotoxicology

Bernd Jastorff

GreenMetrics

Eissen, Metzger,Schmidt,

Schneidewind

GreenMetrics

Eissen, Metzger,Schmidt,

Schneidewind

Green Chemistry/Sustainability ScienceGreen Chemistry/Sustainability ScienceGreen Chemistry: Paul T. Anastas and John C. Warner, Green Chemistry:

Theory and Practice, Oxford University Press, Oxford, 1998.Green Metrics: 10 Years after Rio: Concepts on the Contributions of

Chemistry to a Sustainable Development, Marco Eissen, Jürgen O. Metzger, Eberhard Schmidt and Uwe Schneidewind, Angew. Chem. Int. Ed., 2002, 41, 414-436.

Endocrine Disruption: Our Stolen Future: Are We Threatening Our Fertility, Intelligence, and Survival?—A Scientific Detective Story, Theo Colborn, Dianne Dumanoski, John Peterson Myers.

Toxicity and Ecotoxicity: Joe Thornton, Pandora’s Poison: Chlorine, Health, and a New Environmental Strategy, MIT Press, Cambridge, 2000.

Sustainability Ethics: Hans Jonas, The Imperative of Responsibility: In Search of an Ethics for the Technological Age, Univ. Chicago Press, Chicago, 1984.

History of the Ungreen: Gerald Markowitz and David Rosner, Deceit and Denial: the Ugly Politics of Industrial Pollution,

Terry Collins, Science, 207, 48-49 (2001)

Achieving Sustainable Technologies through Science

Achieving Sustainable Technologies through Science

Technology invented,

sustainability not an issue

Technology invented,

sustainability not an issue

Technology grows in importance - sustainability

issues become evident.

Technology grows in importance - sustainability

issues become evident.

Destabilizing technology becomes a defining feature

of the civilization

Destabilizing technology becomes a defining feature

of the civilization

New Technology invented to resolve sustainability issue

New Technology invented to resolve sustainability issue

Learn to stay in the green regionLearn to stay in the green region

Learn how to analyze greenness

Learn how to analyze greenness

The Energy Research Problem The Energy Research Problem

20th energy research

nuclear fission, fossilized carbon

devastation of sustainability

20th energy research

nuclear fission, fossilized carbon

devastation of sustainability

T.J. Collins, Science, 2001, 291, 1899T.J. Collins, Science, 2001, 291, 1899

20 days of sunlight equals the planetary reserves of oil, coal and natural gas

20 days of sunlight equals the planetary reserves of oil, coal and natural gas

Reproduced with permission of Masaharu Fujinaka, Tokyo Denki UniversityReproduced with permission of Masaharu Fujinaka, Tokyo Denki University

CC

Picture C&E NewsPicture C&E News

SelectivitySelectivity

NatureNature ChemistryChemistry

Small number of elements, supported by elaborate design, sustain the complex chemistryof life

Entire periodic table used to attain selectivity allowing for comparatively simple

reagentdesign

Reducing Persistent PollutantsReducing Persistent Pollutants

Class 1 Elemental toxins; the prototypical persistent pollutants

Class 2

Particularly stable molecular species • chlorine!

Class 1 Elemental toxins; the prototypical persistent pollutants

Class 2

Particularly stable molecular species • chlorine!

T.J. Collins, Science, 2001, 207, 48-49; Nature, 2001, 414, 161

T.J. Collins, Science, 2001, 207, 48-49; Nature, 2001, 414, 161

BioaccumulationBioaccumulation

Atmospheric distillationAtmospheric distillation

Endocrine DisruptionEndocrine Disruption

Limitations of ScienceLimitations of Science

Key Concepts for Understanding How to Deal with Persistent Pollutants

Key Concepts for Understanding How to Deal with Persistent Pollutants

Human LimitationsHuman Limitations

100

101

102

103

104

105

106

107

2000 1000 0 -1000 -2000time / sec

4

3

2

1

0

Lead concentration pg/g

100

101

102

103

104

105

106

107

Lea

d pr

oduc

tion

(ton

s/yr

)

2000 1000 0 -1000yearsYears

Industrial revolution

Discovery of cupellation

Use of coinage

Rise and fall of Athens

Roman republic and empire

Exhaustion of Roman lead

mines

Silver production in

Germany

Spanish production of silver in New

World

Boutron et al. Science, 1994, 265, 1841–1843

Environmental Lead is Mostly AnthropogenicEnvironmental Lead is Mostly Anthropogenic

Lead replaced in paints Lead replaced in paints

Elimination of Et4Pb from fuelsElimination of Et

4Pb from fuels

Safer batteriesSafer batteries

Elimination of lead from piping & solderElimination of lead from piping & solder

Examples of The Greening of Lead Technologies–All by ReplacementExamples of The Greening of Lead Technologies–All by Replacement

Replacement of Pb reagents in synthesisReplacement of Pb reagents in synthesis

ca. 20 M tonnes of lead produced annuallyca. 20 M tonnes of lead produced annually

Antarctic Ozone Hole Antarctic Ozone Hole

www.atm.ch.cam.ac.uk/tour/www.atm.ch.cam.ac.uk/tour/

CFC-115 C

2ClF

5

CFC-115 C

2ClF

5

182418241980s-90s1980s-90s18351835

185018501850Š19281850Š1928

19131913

Nicolas Carnot (1796-1832)

ŠCarnot Theory

Nicolas Carnot (1796-1832)

ŠCarnot Theory

Jacob Perkins patents ether-based

ice-maker

Jacob Perkins patents ether-based

ice-maker

Different refrigerants tested in marketplace - many problemsDifferent refrigerants tested in marketplace - many problems

1928192819741974

1982198219871987

A.C.Twinning �Š 1 ton/day ice

machine

A.C.Twinning �Š 1 ton/day ice

machine

DOMELRE Š first domestic

machine

DOMELRE Š first domestic

machine

Refrigerant properties of CFCÕs discovered

Refrigerant properties of CFCÕs discovered

Roland and Molina

Roland and Molina

Farman discovers Antarctic Ozone Hole

Farman discovers Antarctic Ozone Hole

Montreal ProtocolMontreal Protocol

HCFCs and HFCsHCFCs and HFCs

Limitations of Science: Brief History of Refrigeration

Limitations of Science: Brief History of Refrigeration

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)

CCCC

CCCC

CC

CC CC CC

CC

CC

CCCC

HH HH

HH HH

OO

OO

ClCl

ClCl

ClCl

ClCl

O

O

O

1

2

3

46

7

8

9

98

7

6 4

3

21

Chlorinated Dibenzodioxin

Chlorinated Dibenzodifuran(Substituents 1-4 and 5-9 = H, Cl;

2,3- and 7-8-chlorinated species are toxic)

Our Stolen Future, Theo Colborn, Dianne Dumanoski, John Peterson Myers, Plume- Penguin, New York, 1997

DioxinDioxinPhotograph and story

by Annie O’Neill November 5, 2000

(with permission of Pittsburgh Post Gazette)

Photograph and story by Annie O’Neill

November 5, 2000 (with permission of

Pittsburgh Post Gazette)

Discovery of Lead PoisoningDiscovery of Lead Poisoning

Bastionof Ulm

• 1690s, Ulm colic outbreak—city physician, Eberhard Gockel, notes monks who abstained from wine were healthy– two visiting monks recovered upon returning to their home monastery. Göckel visited daily accepting wine—soon developed colic symptoms.

Sweet Poison Josef Eisinger, Natural History, 7/96

• The wine had been “corrected” by adding a concoction formed by dissolving litharge,PbO, in a quantity of wine and boiling it down to a sweet extract, which Gockel noted turned the worst and sourest wine into the “best and loveliest.”

• 100s of wagon loads of wine from the Neckar River Valley arrived at Ulm’s markets daily for shipment down the Danube. The city’s economy was threatened when the people began blaming colic on wine from Ulm.

• In 1696, Duke Eberhard Ludwig issued an edict banning all lead-based wine additives—possibly the first consumer- protection legislation targeting a specific toxin — it prescribed death for perpetrators and anyone failing to whistle-blow.

TCDD elicits a diverse spectrum of biological sex-, strain-, age-, and species-specific effects, including carcinogenicity, immunotoxicity, reproductive/developmental toxicity, hepatotoxicity, neurotoxicity, chloracne, and loss of body weight. These effects vary according to the age, sex, species, and strain of the animals involved.

TCDD elicits a diverse spectrum of biological sex-, strain-, age-, and species-specific effects, including carcinogenicity, immunotoxicity, reproductive/developmental toxicity, hepatotoxicity, neurotoxicity, chloracne, and loss of body weight. These effects vary according to the age, sex, species, and strain of the animals involved.

Toxicity of TCDDToxicity of TCDD

January 2001 - TCDD designated by USEPA as a known human carcinogen January 2001 - TCDD designated by USEPA as a known human carcinogen

Veterans and Agent Orange, Update 1996, Committee to Review the Health Effects in Vietnam Veterans of Exposure to Herbicides, Division of Health Promotion and Disease Prevention, Institute of Medicine, National Academy Press, Washington, D.C.

Veterans and Agent Orange, Update 1996, Committee to Review the Health Effects in Vietnam Veterans of Exposure to Herbicides, Division of Health Promotion and Disease Prevention, Institute of Medicine, National Academy Press, Washington, D.C.

Lou Guilette, Lake Apopka, Fl; >60% male aligators have

miniaturized sex organs

Lou Guilette, Lake Apopka, Fl; >60% male aligators have

miniaturized sex organs

1950s1950searly 90searly 90s5252

mid-60smid-60s early-70searly-70s1980s1980s

England; otters die off

England; otters die off

Great Lakes; fur-farmers

lose lakefish- fed minks

Great Lakes; fur-farmers

lose lakefish- fed minks

Mike Gilbertson, Lake Ontario;

deformaties and wasting in herring

gull chicks of Near Island

Mike Gilbertson, Lake Ontario;

deformaties and wasting in herring

gull chicks of Near Island

Ralph Schreider, Channel Islands of S. CA; female Western

gulls co-nesting

Ralph Schreider, Channel Islands of S. CA; female Western

gulls co-nesting

Northern Europe;

largest seal die-off in history

Northern Europe;

largest seal die-off in history

A Timeline of Endocrine Disruption

A Timeline of Endocrine Disruption

Our Stolen Future, Theo Colborn, Dianne Dumanoski, John Peterson Myers, Plume-Penguin, NY, 1997

7070

Charles Broley, Gulf Coast, Fl;

golden eagles lose instinct to mate &

raise young

Charles Broley, Gulf Coast, Fl;

golden eagles lose instinct to mate &

raise young

1992199219881988

Mediterranean; massive dieoff of striped dophins -

Alex Anguilar links to PCBs

Mediterranean; massive dieoff of striped dophins -

Alex Anguilar links to PCBs

Niels Skakkeback, Copenhagen; male sperm

counts dropped by almost 50% 1939-1990

Niels Skakkeback, Copenhagen; male sperm

counts dropped by almost 50% 1939-1990

Endocrine DisruptionEndocrine DisruptionCell membraneCell membrane

Natural hormone

Unoccupied Receptor

PollutantPollutant

Pandora’s Poison: Chlorine, Health and a New Environmental Strategy, Joe Thornton, 2000, MIT Press, Cambridge MA

Pandora’s Poison: Chlorine, Health and a New Environmental Strategy, Joe Thornton, 2000, MIT Press, Cambridge MA

Expression of hormone-responsive genes

Block expression of hormone-responsive genes

Anti-hormone effectAnti-hormone effect

Hormone-like effectHormone-like effect

– or –– or –

Two important

mechanisms of endocrine

disruption

Two important

mechanisms of endocrine

disruption

Monsanto study becomes centerpiece of Australian position towards veterans

Monsanto study becomes centerpiece of Australian position towards veterans

19621962 198919891965–691965–69 19701970 1980–841980–8419861986

Military begins spraying agent

orange in Nth. Vietnam

Military begins spraying agent

orange in Nth. Vietnam

Spraying expands Spraying expands

Spraying stops –2,4,5-T found to cause birth

defects in mice

Spraying stops –2,4,5-T found to cause birth

defects in mice

Veterans blame postwar ailments on TCDD in 2,4,5-T

Veterans blame postwar ailments on TCDD in 2,4,5-T

Monsanto releases epidemiological

studies of workers in Nitro,WV plant

Monsanto releases epidemiological

studies of workers in Nitro,WV plant

Monsanto’s Chief Medical Officer concedes Nitro studies flawed

Monsanto’s Chief Medical Officer concedes Nitro studies flawed

Human Limitations: Monsanto and TCDDHuman Limitations:

Monsanto and TCDD

Pandora’s Poison: Chlorine, Health and a New Environmental Strategy, Joe Thornton, 2000, MIT Press, Cambridge MA

Water, 1xWater, 1x

Zooplankton, 6,400xZooplankton, 6,400x

Lanternfish, 170,000xLanternfish, 170,000x

Squid, 240,000xSquid, 240,000x

Striped dolphin, 13,000,000xStriped dolphin, 13,000,000x

Pandora’s Poison (p. 26) from Tatsukawa R. and Tanabe S. “Fate and bioaccumulation of persistent organic chlorine compounds in the marine environment”. In: Baumgartner, D.J., Dudall, I.M., eds, Oceanic Processes in Marine Pollution, Volume 6. Malabar, FL: Krieger, 1990: 39-55 Pandora’s Poison (p. 26) from Tatsukawa R. and Tanabe S. “Fate and bioaccumulation of persistent organic chlorine compounds in the marine environment”. In: Baumgartner, D.J., Dudall, I.M., eds, Oceanic Processes in Marine Pollution, Volume 6. Malabar, FL: Krieger, 1990: 39-55

Biomagnification of PCB’s in the North Pacific Food Chain Biomagnification of PCB’s in the North Pacific Food Chain

US Est. Dioxin Emissions [1995] US Est. Dioxin Emissions [1995] Backyard trash

burning 19%

Backyard trash burning

19%Landfill fires

19%Landfill fires

19%

Incineration 31%

Incineration 31%Cement kilns

3%Cement kilns

3%Other 5%

Other 5%

Nonincinerated municipal sludge 4%

Nonincinerated municipal sludge 4%

Forest, brush & straw fires 3%

Forest, brush & straw fires 3%

Power/energy generation 3%Power/energy generation 3%

Nonferrous metal smelting

11%

Nonferrous metal smelting

11%

USEPA, from C&E News, May 28, 2001, 25–27USEPA, from C&E News, May 28, 2001, 25–27

5,152 TEQ5,152 TEQ

Hydrogen Peroxide:an Ideal Green Reagent

Major industrial oxidant used primarily in non-

catalyzed processes > 1.3 M tonnes annually

Major industrial oxidant used primarily in non-

catalyzed processes > 1.3 M tonnes annually

Key biochemical oxidant in enzymatic processes—P-450s &

peroxidases

Key biochemical oxidant in enzymatic processes—P-450s &

peroxidases

New catalyzed H2O2

processes have immense potential in green and

end-of-pipe applications

New catalyzed H2O2

processes have immense potential in green and

end-of-pipe applications

New catalysts: nontoxic, inexpensive, selective, disposable, fast-acting,

energy-saving

New catalysts: nontoxic, inexpensive, selective, disposable, fast-acting,

energy-saving

UrgentUrgent Not urgentNot urgent

iimm

rroo

nnttaa

pp

tt

ttooNN

mm

rroo

nnttaa

ppII

tt

Necessity Here we do

what we genuinely must.

Necessity Here we do

what we genuinely must.

Originality Here we define our authenticity and frame the

original work we are capable of.

Originality Here we define our authenticity and frame the

original work we are capable of.

DeceptionHere we let

systems steal our chances to be authentic.

DeceptionHere we let

systems steal our chances to be authentic.

Waste Here we

squander our chances to be

authentic.

Waste Here we

squander our chances to be

authentic.

Escaping Urgency Addition: How should universities

confront sustainability?

Escaping Urgency Addition: How should universities

confront sustainability?

UrgentUrgent Not urgentNot urgent

iimm

rroo

nnttaa

pp

tt

ttooNN

mm

rroo

nnttaa

ppII

tt

Necessity

Short-term thinking

Necessity

Short-term thinking

Originality

Long-term thinking

Sustainability

Originality

Long-term thinking

Sustainability

Deception

Short-term thinking

Industrial labs

Deception

Short-term thinking

Industrial labs

Waste

Nonthinking

Waste

Nonthinking

Urgency Addiction: Chemistry

Urgency Addiction: ChemistryJust as it is the bane of professional life, urgency addiction

could suffocate the healthy

scientific pursuit of sustainability

Just as it is the bane of professional life, urgency addiction

could suffocate the healthy

scientific pursuit of sustainability

UrgentUrgent Not urgentNot urgent

iimm

rroo

nnttaa

pp

tt

ttooNN

mm

rroo

nnttaa

ppII

tt

Necessity

Necessity • secure your dominion

(tenure) • collect adequate

resources • recruit great

coworkers • publish adequately

Originality

Originality • focus research energy

strategically on great sustainability problems

• integrate sustainability ethics into research

• create new sustainable economies!

Deception • “publish or perish” in

place of “do important work”

• turn green chemistry into another resource collection exercise

Waste

???

How should university chemists change to deal with

sustainability?

How should university chemists change to deal with

sustainability?

Limitations of Science: The Ecosphere as a Postal NetworkLimitations of Science: The Ecosphere as a Postal Network

Persistent PollutantPersistent Pollutant

T.J. Collins, Science, 291, 48-49 (2001)T.J. Collins, Science, 291, 48-49 (2001)