Barbara Karn, PhDUS EPA

iNEMI workshop

The views presented here are those of the speaker and should not be taken to represent official EPA policy.

Thoughts on EPA, Electronics, and Elemental Nanotechnology-An

Emerging Sustainability Problem

Wednesday, February 23, 2011 Chandler, AZ

About EPA with a little sustainability

Electronics programs in EPA, a bit elsewhere, and some areas of cooperation

Nanomaterials, electronics, elements of concern

Outline

To protect the environment and human health

EPA's Mission:

Goal 1: Taking Action on Climate Change and Improving Air Quality

Goal 2: Protecting America’s Waters

Goal 3: Cleaning Up Communities and Advancing Sustainable

Development

Goal 4: Ensuring the Safety of Chemicals and Preventing Pollution

Goal 5: Enforcing Environmental Laws

EPA’s Strategic Goals 2011-2015

Expanding the Conversation on Environmentalism

Working for Environmental Justice and Children’s Health

Advancing Science, Research, and Technological Innovation

Strengthening State, Tribal, and International Partnerships

Strengthening EPA’s Workforce and Capabilities

Science

Transparency,

Rule of Law

Cross-Cutting Fundamental Strategies

Core Values:

EPA Organizational Structure

Assistant Administrator for

Chemical Safety and Pollution

Prevention

ORD Locations

a

Cincinnati, OH

Narragansett, RI

Research TrianglePark, NC

Athens, GALas Vegas, NV

Duluth, MN

Washington, DC

Gulf Breeze, FLAda, OK

Corvallis, OR

Edison, NJ

Newport, OR

Grosse l le, MI

3 National Laboratories

2 National Centers

2 Offices

13 Locations

6

Extramural grants in all

research areas

National Risk Management

Research Lab

Preventing and reducing risks to

humans and the environment

National Center for

Environmental Research

National Center for

Environmental AssessmentHuman health and ecological

risk assessment

National Homeland Security

Research CenterResponses to attacks against buildings

and water treatment systems

National Exposure Research

Laboratory

Human and ecosystem

exposure to pollutants

National Center for

1. Computational ToxicologyMerging of computational and

molecular approaches

National Health and Environmental

Effects Research Lab

Effects of contaminants

on human health and ecosystems

ORD

ORD aligns its research programs into four integrated research areas and two targeted research areas:

1. Safer Products for a Sustainable World

2. Safe and Sustainable Water

3. Air/Climate/Energy

4. Sustainable Communities: Built and Natural

Environments

5. Human Health Risk Assessment

6. National Homeland Security Research Center

• “Development that meets the needs of the present without compromising the ability of future generations to meet their needs” *1+

• “The reconciliation of society’s developmental goals with the planet’s environmental limits over the long term” *2]

• “Meeting fundamental human needs while preserving the life-support systems of planet Earth” *3+

[1.] The Brundtland Report*2.+ NRC, “Our Common Future”[3.] Kates, RW, et. al., (2001) Science: 292 pp. 641-642.

Sustainability

ECONOMY

SOCIETY

ENVIRONMENT

DEPENDENCIES

ECONOMY

SOCIETY

Giddings et al, Sust. Dev.,2002

SUSTAINABILITY AS

Action Items for Sustainability Science

Accelerate current trends in fertility reduction.

Accommodate an expected doubling to tripling of the urban system

in a habitable, efficient, and environmentally friendly manner.

Reverse declining trends in agricultural production in Africa;

sustain historic trends elsewhere.

Accelerate improvements in the use of energy and materials.

Restore degraded ecosystems while conserving biodiversity elsewhere.

Take Note: Achievements in one sector do not imply

improvements in other sectors or in the situation

overall.

Our Common Journey, National Academy of Science 2000

NCER’s Science to Achieve Results program funds research grants,cooperative agreements, and fellowships in numerous environmental science and engineering disciplines.

Science to Achieve Results - STAR

* air toxics & health effects of particulate matter* drinking water & water quality* global change* ecosystem assessment & restoration* human health risk assessment* endocrine disrupting chemicals* pollution prevention & new technologies* children’s environmental health* economics & decision sciences* computational toxicology* nanotechnology* biomarkers

STAR RFAs have focused on:

EPA Programs in Electronics

13

Energy Star program EPA and DOE

IEEE Standard 1680

ENERGY STAR Version 5.0 Specification for ComputersFinalized November 14, 2008, effective July 2010

EPEAT registration: Desktops, laptops monitors that meet 23 required criteria

2008 goal to avoid 19.4 tonnes C equivalents

EPEAT

14

Life cycle impacts of Li Ion Batteries, including single walled CNT

Environmental and human health attributes of selected flame retardants used in printed circuit boards.

Lead-Free Solder

Printed Wiring Boards

Life Cycle Assessment of desktop computer displays

EPA’s Design for the Environment ProgramSample projects

15

Voluntary Responsible Recycling Practices for Electronics RecyclersR2 Standard

Accredited under ANSI board since 2009

Standard includes:

--using an environmental, health, and safety management system--minimizing exposures or emissions during recycling operations--promoting reuse and material recovery

16

E-Steward program – a waste processors pledge

Basel Action Network

The following electronic parts are considered hazardous under Basel definitions:

- Cathode ray tubes ( [CRTs]- the glass tubes in many monitors and TVs), leaded glass cullet from CRTs, and anything containing CRTs or leaded glass (due to lead content)

- Circuit boards, both high-value and low-value boards, and anything containing them (due to lead and beryllium content)

-Any components containing mercury and/or PCBs

-Any components or material containing beryllium

- Any battery containing lead, cadmium or mercury or a component containing such a battery.

Caution about plastics containing brominated flame retardants

17

Federal activities in Last congress

24 states with 65% of the population of the U.S. is now covered

www.electronicstakeback.com

States are doing their own thing

iNEMI 7 Categories for roadmap

Manufacturing Processes Systems Integration Energy Environment Materials & Reliability Design Information Management

Reduce energy and materials use from ―cradle to cradle.

driving designmaterials substitutiondematerialization

Focus on electronics to help solve climate change

EPA iNEMI

Applications/Implications

AREAS for Cooperation

Rare Earth Metals Assessment and Supply Chain Actions Project

Nanotech-enabled— Semiconductor technologies (Organic Semiconductors, CMOS Sensors )

Memory and storage (Magnetic Heads, Optical Pickup, AFM-based Memory, CNT-based

Memory, Molecular Memory )

Display technologies (Photonic FED, Organic Electroluminescence, Electronic Paper)

Optic/photonic technologies (Photonic Crystal Fiber, Optical Waveguides, Optoelectronic IC)

Energy technologies (Fuel Cells, Li-Ion Batteries, Electric Double-Layer Capacitors,

Microcrystalline Thin Films, Solar Cells, Dye-sensitized Solar Cells)

Bio/health (Drug Delivery Systems, Immunochromatography, Regenerative Medicine,

Biosensors, Drugs)

Materials (nano-composites for airplane, automobile bodies and parts)

Chemical processing (Nano-scaled catalysts, nano-membranes)

Consumer products (sports equipment, cosmetics, textiles, appliances, food additives

Major uses of nanomaterials in products

What do we know about their health and environmental impacts?

21

Growth of Elements in Electronics

Elemental Composition of a Human

The Biosphere

Oxygen, 46.00%

Silicon, 27.00%

Aluminum, 8.10%

Iron, 6.30%

Calcium, 5.00%

Magnesium, 2.90% Sodium, 2.30%

Potassium, 1.50%

Titanium, 0.66%

Carbon, 0.18% Hydrogen, 0.15% Manganese, 0.11%

Phosphorus, 0.10%

Oxygen

Silicon

Aluminum

Iron

Calcium

Magnesium

Sodium

Potassium

Titanium

Carbon

Hydrogen

Manganese

Phosphorus

Elemental Composition of Lithosphere

Human % Crust %

oxygen 61.353 46.000

carbon 22.829 18.000

hydrogen 9.988 0.150

nitrogen 2.568 0.002

calcium 1.427 5.000

phosphorus 1.113 0.001

potassium 0.200 1.500

sulfur 0.200 0.042

rest 0.322 47.026

Elemental Content

Elements used in nanomaterials

Modified from Robichaud et al, 2009

ss

Life cycle of nanomaterials

DOE 2010

Use of Elements in Energy Applications

(DOE, 2010)

Critical Energy Elements

Focus on an Element

Indium’s abundance in the continental crust is estimated to be approximately 0.05 part per million. Trace amounts of indium occur in base metal sulfides—particularly chalcopyrite, sphalerite, and stannite—by ionic substitution. Indium is most commonly recovered from the zinc-sulfide ore mineral sphalerite. The average indium content of zinc deposits from which it is recovered ranges from less than 1 part per million to 100 parts per million. Although the geochemical properties of indium are such that it occurs with other base metals—copper, lead, and tin—and to a lesser extent with bismuth, cadmium, and silver, most deposits of these metals are subeconomic for indium.

Vein stockwork deposits of tin and tungsten host the highest known concentrations of indium. However, the indium from this type of deposit is usually difficult to process economically. Other major geologic hosts for indium mineralization include volcanic-hosted massive sulfide deposits, sediment-hosted exhalative massive sulfide deposits, polymetallic vein-type deposits, epithermal deposits, active magmatic systems, porphyry copper deposits, and skarndeposits.

Import Sources (2004-07):1 China, 43%; Japan, 18%; Canada, 17%; Belgium, 7%; and other, 15%.

Tolcin, U.S. Geological Survey, Mineral Commodity Summaries, January 2009

(tonnes)

Indium Stats

Primary Indium:

Supply vs. Demand

• 2004: 509mt

• 2005: 630mt

• 2006: 750mt

0

100

200

300

400

500

600

700

800

2003 2004 2005 2006

Demand Supply Capacity

X

O’Neill, 2004

Mining, mainly from Zinc mines as sphalerite

Australian Zn mine

Chinese Zn mine

Extracting Indium

--Leaching in H2SO4 or HCl; purifying leach solution using In strips to get sponge of crude In. Extracting with solvent of tributyl phosphate or bis(2-ethylhexyl)-phosphoric acid

--Precipitation of InPO4 from slightly acidic solution. Conversion of phosphate to oxide using NaOH. Reduction of oxide to In metal

--For Zn retort smelting, In distilled with Zn and concentrates in molten Zn-Pb metal at bottom during 1st stage evaporation and reflux purification of Zn. In is separated as high grade slag and recovered by leaching and sponging as above.

Sponge In (99 to 99.5% pure) refined via soluble-anode electrolysis.

Anthony John Downs, 1993

Australian Zinc Smelter

Refinery production (tonnes)2007 2008 est.

United States — —Belgium 30 30Canada 50 50China 320 330 France 10 —Japan 60 60Korea, Republic of 50 50Peru 6 6Russia 12 12Other countries 25 30World total (rounded) 563 568

Production

Tolcin, U.S. Geological Survey, Mineral Commodity Summaries, January 2009

US uses 28%

Flat panel display applications for

indium tin oxide: Liquid crystal

displays; Plasma display panels;

Electrochromic displays; Field

emission displays; LEDs

Uses Of Indium

Mobile telephones, Computer monitors, Televisions, Watches and calculators, Digital video and still cameras

Thin-film photovoltaics (Cu-In-Ga-Se : CIGS)—Flexible solar cells for roofing or other power applications

An LCD manufacturer has developed a process to reclaim indium directly from scrap LCD panels. The panels are crushed into millimeter-sized particles then soaked in an acid solution to dissolve the ITO, from which the indium is recovered. Indium recovery from tailings was thought to have been insignificant, as these wastes contain low amounts of the metal and can be difficult to process.

However, recent improvements to the process technology have made indium recovery from tailings viable when the price of indium is high.

End of life

Tolcin, U.S. Geological Survey, Mineral Commodity Summaries, January 2009

In Japan 470 t-In is used in ITO for transparent electrodes,

out of which 220 t-In (47%)is dissipated or potentially dissipated

NAKAJIMA et al, 2007

End of life

NF3 – Greenhouse gas with large potential impact

ITO - Main form of In for flat screens

Impactful Ingredients

Health considerations

“These results (40 men in indium plant) suggest that inhaled indium compounds can cause pulmonary disorders such as interstitial changes.”

Nogami et al 2008

Case of interstitial pneumonia from ITO

Homma 2003

Pulmonary and testicular toxicity to hamsters

Tanaka et al 2002

Omura et al 2002

…indium showed teratogenicity in rats (and rabbits, Ungvary,2000). Oral treatment with indium may be developmentally toxic at 300 mg In/kg

Nakajima, 1998

Indium caused tail malformations in rats

Nakajima, 2008

Kidney impairment ICSC:1293

Cummings, 2010

Worker death and pulmonary auto immune response in ITO facility

Food for thought

The lifecycle of uncommon elements used in nanomaterialsneeds attention.

We know little about their human health effectsand less about their environmental effects.

The end of life will likely be dissipative.

Their extraction/processing is environmentally costly.

Production and use impacts are unrecognized and/or unknown.

Bottom Line

There is a vast opportunity to be proactive and preventive by

examining impacts of unusual elements now.

?Questions

Barbara KarnKarn.Barbara@epa.gov

"It is not who is right, but what is right that is of importance." T. Huxley

DOE’s Key Materials

DOE 2010

Key materials Production and Reserves

Major product Co- or byproduct

Nickel, copper Cobalt Copper Tellurium Zinc Indium, gallium Higher profit rare earth elements (Nd) Lower profit rare earth elements (La, Ce, Sm)

Indium is most commonly recovered from ITO. Sputtering, the process in which ITO is deposited as a thin-film coating onto a substrate, is highly inefficient; approximately 30% of an ITO target is deposited onto the substrate. The remaining 70% consists of the spent ITO target, the grinding sludge, and the after-processing residue left on the walls of the sputtering chamber. It was estimated that 60% to 65% of the indium in a new ITO target will be recovered, and research was underway to improve this rate further.

A short recycling process time for used ITO targets is critical as a recycler may have millions of dollars worth of indium in the recycling loop at any one time, and a large increase in ITO scrap could be problematic owing to large capital costs, environmental restrictions, and limited storage space. It was reported that the ITO recycling loop—from collection of scrap to production of secondary materials—now takes less than 30 days. ITO recycling is concentrated in China, Japan, and the Republic of Korea—the countries where ITO production and sputtering take place.

End of life

Tolcin, U.S. Geological Survey, Mineral Commodity Summaries, January 2009