NANO TECHNOLOGY

in

Submitted by

VAMSHI KRISHNA PATHA

+
(NAAC Accredited with ‘A ’ Grade & NBA Accredited)
(Approved by AICTE, Permanently Affiliated to JNTU Hyderabad)
KANDLAKOYA, MEDCHAL ROAD, HYDERABAD-501401

2021-22

i|Page
 +
(NAAC Accredited with ‘A ’ Grade & NBA Accredited)
(Approved by AICTE, Permanently Affiliated to JNTU Hyderabad)

KANDLAKOYA, MEDCHAL ROAD, HYDERABAD-501401

This is to certify that the technical seminar report entitled “NANO TECHNOLOGY”

Bonafide work done by in partial fulfilment of the requirements

for the award of the degree of Bachelor of Technology in Electrical & Electronics Engineering, submitted
to the Department of Electrical & Electronics Engineering, CMR College of Engineering & Technology,
Hyderabad during the Academic Year2022-23.

Prof. K.SOUJANYA

HOD, EEE Department

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I am obliged and grateful to thank, Mrs . Department of EEE,
CMRCET for her cooperation in all respects.

I would like to thank Major , Principal, CMRCET, for his support in the
course of this technical seminar.

I would like to thank Sri garu, Secretary& Correspondent of CMRCET, for

his cooperation in all respects during the course.

Finally, I would like to thank all teaching & non- teaching staff members of the
department, for their cooperation and support throughout the duration of our course.

VAMSHI KRISHNA PATHA

(20H55A0216)

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 Table of Contents
FOREWORD ................................................................................................................................................... VIII
ACKNOWLEDGMENTS................................................................................................................................... IX
ACRONYMS......................................................................................................................................................... X
EXECUTIVE SUMMARY ................................................................................................................................... 1
1.0 INTRODUCTION ........................................................................................................................................... 4
1.1 PURPOSE ........................................................................................................................................................................................................ 4
1.2 NANOTECHNOLOGY DEFINED ............................................................................................................................................................. 5
1.3 WHY NANOTECHNOLOGY IS IMPORTANT TO EPA ...................................................................................... 13
1.4 NATIONAL AND INTERNATIONAL CONTEXT ............................................................................................................................... 14
1.5 WHAT EPA IS DOING WITH RESPECT TO NANOTECHNOLOGY .......................................................................................... 18
1.6 OPPORTUNITIES AND CHALLENGES................................................................................................................................................. 21
2.0 ENVIRONMENTAL BENEFITS OF NANOTECHNOLOGY ...............................................................22
2.1 INTRODUCTION ........................................................................................................................................................................................ 22
2.2 BENEFITS THROUGH ENVIRONMENTAL T ECHNOLOGY APPLICATIONS........................................................................... 22
2.3 BENEFITS THROUGH OTHER APPLICATIONS THAT SUPPORT SUSTAINABILITY .......................................................... 24
3.0 RISK ASSESSMENT OF NANOMATERIALS.........................................................................................29
3.1 INTRODUCTION ........................................................................................................................................................................................ 29
3.2 CHEMICAL IDENTIFICATION AND CHARACTERIZATION OF NANOMATERIALS ............................................................ 31
3.3 ENVIRONMENTAL FATE OF NANOMATERIALS ........................................................................................................................... 32
3.4 ENVIRONMENTAL DETECTION AND ANALYSIS OF NANOMATERIALS ............................................................................. 40
3.5 HUMAN E XPOSURES AND T HEIR MEASUREMENT AND CONTROL .................................................................................... 42
3.6 HUMAN HEALTH EFFECTS OF NANOMATERIALS ..................................................................................................................... 52
3.7 ECOLOGICAL E FFECTS OF NANOMATERIALS.............................................................................................................................. 58
4.0 RESPONSIBLE DEVELOPMENT ............................................................................................................ 63
4.1 RESPONSIBLE DEVELOPMENT OF NANOSCALE M ATERIALS ............................................................................................... 63
4.2 PROGRAM AREAS..................................................................................................................................................................................... 65
4.3 ENVIRONMENTAL STEWARDSHIP ..................................................................................................................................................... 68
5.0 EPA’S RESEARCH NEEDS FOR NANOMATERIALS ......................................................................... 70
5.1 RESEARCH NEEDS FOR E NVIRONMENTAL APPLICATIONS ................................................................................................... 70
5.2 RESEARCH NEEDS FOR RISK ASSESSMENT.................................................................................................................................. 72
6.0 RECOMMENDATIONS .............................................................................................................................. 82
6.1 RESEARCH RECOMMENDATIONS FOR E NVIRONMENTAL APPLICATIONS ...................................................................... 82
6.2 RESEARCH RECOMMENDATIONS FOR RISK ASSESSMENT..................................................................................................... 83
6.3 RECOMMENDATIONS FOR POLLUTION PREVENTION AND ENVIRONMENTAL STEWARDSHIP................................ 89
6.4 RECOMMENDATIONS FOR COLLABORATIONS............................................................................................................................. 90
6.5 RECOMMENDATION TO CONVENE AN INTRA-AGENCY WORKGROUP............................................................................. 91
6.6 RECOMMENDATION FOR TRAINING ................................................................................................................................................ 91
6.7 SUMMARY OF RECOMMENDATIONS ............................................................................................................................................... 92
7.0 REFERENCES .............................................................................................................................................. 93
APPENDIX A: GLOSSARY OF NANOTECHNOLOGY TERMS ............................................................ 107
APPENDIX B: PRINCIPLES OF ENVIRONMENTAL STEWARDSHIP BEHAVIOR......................... 110
APPENDIX C: EPA’S NANOTECHNOLOGY RESEARCH FRAMEWORK......................................... 111
APPENDIX D: EPA STAR GRANTS FOR NANOTECHNOLOGY ......................................................... 113
 5

The purpose of this paper is to inform EPA management of the science needs
associated with nanotechnology, to support related EPA program office needs, and to
communicate these
nanotechnology science issues to stakeholders and the public. The paper begins with an
introduction that describes what nanotechnology is, why EPA is interested in it, and what
opportunities and challenges exist regarding nanotechnology and the environment. It then moves
to a discussion of the potential environmental benefits of nanotechnology, describing
environmental technologies as well as other applications that can foster sustainable use of
resources. The paper next provides an overview of existing information on nanomaterials
regarding components needed to conduct a risk assessment. Following that is a brief section
on responsible development and the Agency’s statutory mandates. The paper then provides an
extensive review of research needs for both environmental applications and implications of
nanotechnology. To help EPA focus on priorities for the near term, the paper concludes with
staff recommendations for addressing science issues and research needs, and includes
prioritized research needs within most risk assessment topic areas (e.g., human health effects
research, fate and transport research). In a separate follow-up effort to this White Paper, EPA’s
Nanotechnology Research Framework, attached in Appendix C of this paper, was developed
by EPA's Office of Research and Development (ORD) Nanotechnology Research Strategy
Team. This team is composed of representatives from across ORD. The Nanotechnology
Research
Framework outlines how EPA will strategically focus its own research program to provide key
information on potential environmental impacts from human or ecological exposure to
nanomaterials in a manner that complements other federal, academic, and private-sector research
activities. Additional supplemental information is provided in a number of additional
appendices.

A discussion of an entire technological process or series of processes, as is

nanotechnology , could be wide ranging. However, because EPA operates through specific
programmatic activities and mandates, this document confines its discussion of
nanotechnology science issues within the bounds of EPA’s statutory responsibilities and
authorities. In
particular, the paper discusses what scientific information EPA will need to
address nanotechnology in environmental decision making.

1 . 2 Nanotechnology Defined
-9
A nanometer is one billionth of a meter (10 m)—about one hundred thousand times
smaller than the diameter of a human hair, a thousand times smaller than a red blood cell, or
about half the size of the diameter of DNA. Figure 1 illustrates the scale of objects in the
nanometer range. For the purpose of this document, nanotechnology is defined as: research and
technology development at the atomic, molecular, or macromolecular levels using a length scale
of approximately one to one hundred nanometers in any dimension; the creation and use of
structures, devices and systems that have novel properties and functions because of their small
size; and the ability to control or manipulate matter on an atomic scale. This definition is based
on part on the definition of nanotechnology used by the National Nanotechnology Initiative
(NNI), a U.S. government initiative launched in 2001 to coordinate nanotechnology research and
development across the federal government (NNI, 2006a,b, c).
5
Figure 1. Diagram indicating relative scale of nanosized objects.
(From NNI website, courtesy Office ofBasic Energy Sciences, U.S. Department of Energy.
 Nanotechnology is the manipulation of matter for use in particular applications
through certain chemical and / or physical processes to create materials with specific
properties. There are both "bottom-up" processes (such as self-assembly) that create
nanoscale materials from atoms and molecules, as well as "top-down" processes (such as
milling) that create nanoscale materials from their macro-scale counterparts. Figure 2 shows
an example of a nanomaterial assembled through “bottom-up” processes. Nanoscale
materials that have macro-scale
counterparts frequently display different or enhanced properties compared to the macro-scale

form. For the remainder of this document such

engineered or manufactured nanomaterials will be
referred to as “intentionally produced nanomaterials,” or
simply “nanomaterials.” The definition of
nanotechnology does not include unintentionally
produced nanomaterials, such as diesel exhaust particles
or other friction or airborne combustion byproducts, or
nanosized materials that occur naturally in the
environment, such as viruses or volcanic ash. Where
information from incidentally formed or natural
nanosized materials (such as ultrafine particulate matter)
may aid in the understanding of intentionally produced
nanomaterials, this information will be discussed, but
the focus of this document is on intentionally
produced nanomaterials.
Figure 2. Gallium Phosphide (GaP)
Nanotrees. There are many types of intentionally produced
Semiconductor nanowires produced by nanomaterials, and a variety of others are expected to
controlled seeding, vapor-liquid-solid
appear in the future. For the purpose of this document,
self-assembly. Bottom-up processes used
to produce materials such as these allow
most current nanomaterials could be organized into
for control over size and morphology. four types:
(Image used by permission, Prof. Lars
Samuelson, Lund University, Sweden.
[Dick et al. 2004])

(1) Carbon-based materials. These nanomaterials are composed mostly of carbon, most
commonly taking the form of a hollow spheres, ellipsoids, or tubes. Spherical and ellipsoidal
carbon nanomaterials are referred to as fullerenes, while cylindrical ones are called nanotubes.
These particles have many potential applications, including improved films and coatings,
stronger and lighter materials, and applications in electronics. Figures 3, 4, and 5 show
examples of carbon-based nanomaterials.
 Figure 3. Computer image of a
C-60 Fullerene. U.S. EPA.

Figure 4. Computer images of Figure 5. “Forest” of aligned carbon nanotubes.

various forms of carbon nanotubes. (Image courtesy David Carnahan of NanoLab, Inc.)
(Images courtesy of Center for
Nanoscale Materials, Argonne National
Laboratory)

(2) Metal-based materials. These nanomaterials include quantum dots, nanogold,

nanosilver and metal oxides,such as titanium dioxide. A quantum dot is a closely packed
semiconductor crystal comprised of hundreds or thousands of atoms, and whose size is on the
order of a few nanometers to a few hundred nanometers. Changing the size of quantum dots
changes their optical properties. Figures 6 and 7 show examples of metal-based
nanomaterials.
 Figure 6. Zinc oxide nanostructure Figure 7. Computer image of a Gallium
synthesized by a vapor-solid process. arsenide quantum dot of 4 6 5 atoms.
(Image courtesy of Prof. Zhong Lin (Image courtesy of Lin-Wang Wang,
Wang, Georgia Tech) Lawrence Berkeley National Laboratory)

(3) Dendrimers. These nanomaterials are nanosized polymers built from branched units.
The surface of a dendrimer has numerous chain ends, which can be tailored to perform specific
chemical functions. This property could also be useful for catalysis. Also, because three-
dimensional dendrimers contain interior cavities into which other molecules could be placed,
they may be useful for drug delivery. Figure 8 shows an example a dendrimer.

Figure 8. Computer image of generations of a dendrimer.

Dendrimers are nanoscale branched polymers that are grown in a stepwise fashion, which
allows for precise control of their size. (Image courtesy of Dendritic NanoTechnologies,
Inc.)
 (4) Composites combine nanoparticles with other nanoparticles
or with larger, bulk-type materials. Nanoparticles, such as
nanosized clays, are already being added to products ranging from
auto parts to packaging materials, to enhance mechanical,
thermal, barrier, and flame-retardant properties. Figure 9
shows an example of a composite.

The unique properties of these various types of

Figure 9. Computer image of a intentionally produced nanomaterials give them novel electrical,
nano-biocomposite. catalytic, magnetic, mechanical, thermal, or imaging features that
Image of a titanium molecule are highly desirable for applications in commercial, medical,
(center) with DNA strands
military, and environmental sectors. These materials may also
attached, a bio-inorganic
find their way into more complex nanostructures and systems as
composite. This kind of
described in Figure 10. As new uses for materials with these
material has potential for new
special properties are identified, the number of products
technologies to treat disease.
(Image courtesy of Center for containing such nanomaterials and their possible applications
Nanoscale Materials, Argonne continues to grow. Table 1 lists some examples of
National Lab) nanotechnology products listed in the Woodrow Wilson Center
Consumer Products Inventory
http://www.nanotechproject .org/44/consumer-nanotechnology (). There are estimates that global
sales of nanomaterials could exceed $ 1 trillion by 2 0 1 5 ( M . C . Roco, presentation to the
National Research Council, 23 March 2005, presentation available at
http :// www . nsf . gov / crssprgm / na no/reports/nnipres.jsp ).
Table 1. Examples of Products that Use Nanotechnology and Nanomaterials

Health and Electronics and Home and Food and Other

Fitness Computers Garden Beverage
Wound dressing Computer Paint Non-stick Coatings
displays coatings for pans
Pregnancy test Antimicrobial Lubricants
Games pillows Antimicrobial
Toothpaste refrigerator
Computer Stain resistant
Golf club hardware cushions Canola oil

Tennis Racket

Skis

Antibacterial
socks

Waste and stain

resistant pants

Cosmetics

Air filter

Sunscreen

Source: Woodrow Wilson Center Consumer Products Inventory.

(http://www.nanotechproject.org/44/consumer-nanotechnology)

1.2.1 Converging Technologies

In the long-term, nanotechnology will likely be increasingly discussed within the context
of the convergence, integration, and synergy of nanotechnology, biotechnology, information
technology,and cognitive technology. Convergence involves the development of novel
products with enhanced capabilities that incorporate bottom-up assembly of miniature
components with accompanying biological, computational and cognitive capabilities. The
convergence of
nanotechnology and biotechnology, already rapidly progressing, will result in the production of
novel nanoscale materials. The convergence of nanotechnology and biotechnology with
information technology and cognitive science is expected to rapidly accelerate in the coming
decades. The increased understanding of biological systems will provide valuable
information towards the development of efficient and versatile biomimetic tools, systems, and
architecture.

Generally, biotechnology involves the use of microorganisms, or bacterial

factories, which contain inherent “blueprints” encoded in the DNA, and a manufacturing
process to
produce molecules such as amino acids. Within these bacterial factories, the organization and
self-assembly of complex molecules occurs routinely. Many “finished” complex cellular
products are < 100 nanometers. For this reason, bacterial factories may serve as models for the
organization, assembly and transformation for other nanoscale materials production.

Bacterial factory blueprints are also flexible. They can be modified to produce novel
nanobiotechnology products that have specific desired physical-chemical (performance)
characteristics. Using this production method could be a more material and energy efficient way
to make new and existing products, in addition to using more benign starting materials. In this
way, the convergence of nano- and biotechnologies could improve environmental protection.
As an example,researchers have extracted photosynthetic proteins from spinach chloroplasts
and
coated them with nanofilms that convert sunlight to electrical current, which one day may lead to
energy generating films and coatings (Das et al., 2004). The addition of information and
cognitive capabilities will provide additional features including programmability,
miniaturization, increased power capacities, adaptability, and reactive, self-correcting capacities.

Another example of converging technologies is the development of nanometer-sized

biological sensor devices that can detect specific compounds within the natural environment;
store, tabulate, and process the accumulated data; and determine the import of the data,
providing a specific response for the resolved conditions would enable rapid and effective human
health
and environmental protection. Responses could range from the release of a certain amount
of biological or chemical compound, to the removal or transformation of a compound.

The convergence of nanotechnology with biotechnology and with information and

cognitive technologies may provide such dramatically different technology products that the
manufacture, use and recycling/disposal of these novel products, as well as the development
of policies and regulations to protect human health and the environment, may prove to be a
daunting task.

The Agency is committed to keeping abreast of emerging issues within the

environmental arena, and continues to support critical research, formulate new policies, and
adapt existing
policies as needed to achieve its mission. However, the convergence of these technologies
will demand a flexible, rapid and highly adaptable approach within EPA. As these
technologies
progress and as novel products emerge, increasingly the Agency will find that meeting
constantly changing demands depends on taking proactive actions and planning.

We may be nearing the end of basic research and development on the first generation
of materials resulting from nanotechnologies that include coatings, polymers, more reactive
catalysts, etc. (Figure 10). The second generation, which we are beginning to enter, involves
targeted drug delivery systems, adaptive structures and actuators, and has already provided some
interesting examples. The third generation, anticipated within the next 10-15 years, is predicted
to bring novel robotic devices, three-dimensional networks and guided assemblies. The fourth
stage is predicted to result in molecule-by-molecule design and self-assembly capabilities.
Although it is not likely to happen for some time, this integration of these fourth-generation
nanotechnologies with information, biological, and cognitive technologies will lead to products
which can now only be imagined. While the Agency will not be able to predict the future, it
needs to prepare for it. Towards that aim, understanding the unique challenges and opportunities
afforded by converging technologies before they occur will provide the Agency with the
essential tools for the effective and appropriate response to emerging technology and science.

Technological Complexity
increasing

First Generation ~2001: Passive nanostructures

Nano-structured coatings, nanoparticles, nanostructured metals, polymers, ceramics,
Catalysts, composites, displays

Second Generation ~ Now: Active nanostructures

Transistors, amplifiers, targeted drugs and chemicals, actuators, adaptive
structures, sensors, diagnostic assays, fuel cells, solar cells, high performance
nanocomposites, ceramics, metals

Third Generation ~ 2010: 3-D nanosystems and systems of nanosystems

Various assembly techniques, networking at the nanoscale and new architectures,

Biomimetic materials, novel therapeutics/targeted drug delivery

Fourth Generation ~2015 Molecular Nanosystems

Molecular devices ”by design”, atomic design, emerging functions

Figure 10. Projected Stages of Nanotechnology Development.

This analyis of the projected stages of nanotechnology development was first conceptualized
by M.C. Roco.

1.3 Why Nanotechnology Is Important to EPA

Nanotechnology holds great promise for creating new materials with enhanced properties
and attributes. These properties, such as greater catalytic efficiency, increased electrical
conductivity, and improved hardness and strength, are a result of nanomaterials’ larger
surface area per unit of volume and quantum effects that occur at the nanometer scale
(“nanoscale”).
Nanomaterials are already being used or tested in a wide range of products such as sunscreens,
composites, medical and electronic devices, and chemical catalysts. Similar to nanotechnology’s
success in consumer products and other sectors, nanomaterials have promising environmental
applications. For example, nanosized cerium oxide has been developed to decrease diesel
emissions, and iron nanoparticles can remove contaminants from soil and ground water.
Nanosized sensors hold promise for improved detection and tracking of contaminants. In
these and other ways, nanotechnology presents an opportunity to improve how we measure,
monitor, manage, and reduce contaminants in the environment.

Some of the same special properties that make nanomaterials useful are also
properties that may cause some nanomaterials to pose hazards to humans and the
environment, under
specific conditions. Some nanomaterials that enter animal tissues may be able to pass through
cell membranes or cross the blood-brain barrier. This may be a beneficial characteristic for
such uses as targeted drug delivery and other disease treatments, but could result in unintended
impacts in other uses or applications. Inhaled nanoparticles may become lodged in the lung or
be translocated, and the high durability and reactivity of some nanomaterials raise issues of
their fate in the environment. It may be that in most cases nanomaterials will not be of human
health or ecological concern. However, at this point not enough information exists to assess
environmental exposure for most engineered nanomaterials. This information is important
because EPA will need a sound scientific basis for assessing and managing any unforeseen future
impacts resulting from the introduction of nanoparticles and nanomaterials into the environment.

A challenge for environmental protection is to helpfully realize the societal benefits of

nanotechnology while identifying and minimizing any adverse impacts to humans or ecosystems
from exposure to nanomaterials. In addition, we need to understand how to best apply
nanotechnology for pollution prevention in current manufacturing processes and in the
manufacture of new nanomaterials and nanoproducts, as well as in environmental detection,
monitoring, and clean-up. This understanding will come from scientific information generated
by environmental research and development activities within government agencies, academia,
and the private sector.

1.4 National and International Context

EPA’s role in nanotechnology exists within a range of activities by federal agencies
and other groups that have been ongoing for several years. Figure 11 lists examples of federal
sources of information and interaction to inform EPA’s nanotechnology activities. Many
sectors, including U.S. federal and state agencies, academia, the private-sector, other national
governments, and international bodies, are considering potential environmental applications and
implications of nanotechnology. This section describes some of the major players in this arena,
for two principal reasons: to describe EPA’s role regarding nanotechnology and the
environment, and to identify opportunities for collaborative and complementary efforts.
 Understanding Nanotechnology Implications
Characterization , Instrumentation, Toxicity
Properties Metrology,
DOD
DOD
Standards EPA
DOE FDA
DOD NIH
EPA
NASA DOE NIOSH
NIH
NASA
NIH
EP NSF
NIST
NIST A
NSF
NSF
Fate, Transport,
Transformation,
Risk assessment
Release,
Risk management Treatment
DOD
DOE
Sustainabi
lity EPA
NIH
NIOSH
NSF

Pollution Remediation Sensors, Detection,

Prevention EPA
Green manufacturing DHS DH
Monitoring
DOD DOD
Green Engineering
DOE S
Green Energy NASA DO DOD
NSF D EPA
EPA DO NIH
E NIOSH
EP NSF
A
USGS
NSF

Applications USDA
USGS
Note: NIH includes NIEHS, NCI (NCL),

Figure 11. Federal Sources to Inform EPA’s Nanotechnology Activities.

( Based on information in the NNI Supplement to the 2 0 0 6 and 2 0 0 7 budget and other information. )

1.4.1 Federal Agencies – The National Nanotechnology Initiative

The National Nanotechnology Initiative (NNI) was launched in 2001 to coordinate
nanotechnology research and development across the federal government. Investments into
federally funded nanotechnology-related activities, coordinated through theNNI, have grown
from $464 million in 2001 to approximately $1.3 billion in 2006.

The NNI supports a broad range of research and development including fundamental
research on the unique phenomena and processes that occur at the nano scale, the design and
discovery of new nanoscale materials, and the development of nanotechnology-based
devices and systems. The NNI also supports research on instrumentation, metrology,
standards, and
nanoscale manufacturing. Most important to EPA, the NNI has made responsible development
of this new technology a priority by supporting research on environmental health and safety
implications.

Twenty-five federal agencies currently participate in the NNI, thirteen of which have
budgets which include to nanotechnology research and development. The other twelve agencies
have made nanotechnology relevant to their missions or regulatory roles. Only a small part of
this federal investment aims at researching the social and environmental implications of
nanotechnology including its effects on human health, the environment, and society. Nine
federal agencies are investing in implications research including the National Science
Foundation, the National Institutes of Health, the National Institute for Occupational Health
and Safety, and the Environmental Protection Agency. These agencies coordinate their efforts
through the NNI’s Nanoscale Science, Engineering, and Technology Subcommittee (NSET) and
its Nanotechnology Environmental Health Implications workgroup (NEHI) (Figure 12). The
President’s Council of Advisors on Science and Technology (PCAST) has been designated as
st
the national Nanotechnology Advisory Panel called for by the 21 Century Nanotechnology
Research and Development Act of 2003. As such, PCAST is responsible for assessing
and making recommendations for improving the NNI, including its activities to address
environmental and other societal implications. The National Research Council also
provides assessments and advice to the NNI.

Work under the NNI can be monitored through the website http://www.nano.gov.

NSET Subcommittee Working Level Interactions

National Research Office of Science and

24 Agencies Participating in NNI Technology Policy
Council
NEHI
NNAP (PCAST) WG Office of Management
and Budget

International G
I NNCO
Organizations
NSET
Subcomm
Press House of Representatives
NP Committee on Science
Professional EG
Societies
Senate Committee on
Commerce, Science and
Non-governmental Transportation
Organizations NI
LI Working Groups
Regional, State, and Local
Industry Sectors and
Nanotechnology Initiatives
Subcommittee

NRC Review of the NNI August 25-26, 2005

ECTeague NNCO/ NSET/

Figure 12. NNI NSET Subcommittee Structure

1.4.2 Efforts of Other Stakeholders

About $2 billion in annual research and development investment are being spent by non-
federal U.S. sectors such as states, academia, and private industry. State governments
collectively spent an estimated $400 million on facilities and research aimed at the development
of local nanotechnology industries in 2004 (Lux Research, 2004).
 Although the industry is relatively new, the private sector is leading a number of
initiatives. Several U.S. nanotechnology trade associations have emerged, including the
NanoBusiness Alliance. The American Chemistry Council also has a committee devoted to
nanotechnology and is encouraging research into the environmental health and safety of
nanomaterials. In addition, the Nanoparticle Occupational Safety and Health Consortium has
been formed by industry to investigate occupational safety and health issues associated with
aerosol nanoparticles and workplace exposure monitoring and protocols. A directory of
nanotechnology industry-related organizations can be found at http://www.nanovip.com .

Environmental nongovernmental organizations (NGOs) such as Environmental Defense,

Greenpeace UK, ETC Group, and the Natural Resources Defense Council are engaged in
nanotechnology issues. Also, scientific organizations such as the National Academy of Sciences,
the Royal Society of the United Kingdom, and the International Life Sciences Institute are
providing important advice on issues related to nanotechnology and the environment.

1.4.3 International Activities

Fully understanding the environmental applications and implications of

nanotechnology will depend on the concerted efforts of scientists and policy makers across the
globe. Europe and Asia match or exceed the U.S. federal nanotechnology research budget.
Globally,
nanotechnology research and development spending is estimated at around $9 billion (Lux
Research, 2006). Thus, a great opportunity exists for internationally coordinated and integrated
efforts toward environmental research. Other governments have also undertaken efforts to
identify research needs for nanomaterials (United Kingdom (UK) Department for Environment,
Food and Rural Affairs, 2005; European Union Scientific Committee on Emerging and Newly
Identified Health Risks (EUSCENIHR), 2005). International organizations such as the
International Standards Organization and the Organisation for Economic Co-operation and
Development (OECD) are engaged in nanotechnology issues. ISO has established a technical
committee to develop international standards for nanotechnologies. This technical committee,
ISO/TC 229 will develop standards for terminology and nomenclature, metrology and
instrumentation, including specifications for reference materials, test methodologies, modeling
and simulation, and science-based health, safety and environmental practices.

The OECD has engaged the topic of the implications of manufactured nanomaterials
among its members under the auspices of the Joint Meeting of the Chemicals Committee and
Working Party on Chemicals, Pesticides and Biotechnology (Chemicals Committee). On the
basis of an international workshop hosted by EPA in Washington in December 2005,the Joint
Meeting has agreed to establish a subsidiary body to work on the environmental health and
safety implications of manufactured nanomaterials, with an eye towards enhancing
international harmonization and burden sharing. In a related activity, the OECD’s Committee
on Scientific and Technology Policy is considering establishing a subsidiary body to address
other issues
related to realizing commercial and public benefits of advances in nanotechnology.

Additionally, the United States and European Union Initiative to Enhance Transatlantic
Economic Integration and Growth (June 2005) addresses nanotechnology. Specifically, the
Initiative states that the United States and the European Union will work together to, among
other things, “support an international dialogue and cooperative activities for the responsible
development and use of the emerging field of nanotechnology.” EPA is also currently
working with the U.S. State Department, theNNI, and the EU to bring about research
partnerships in
nanotechnology. Furthermore, in the context of environmental science, the EPA has worked
with foreign research institutes and agencies (e.g., UK and Taiwan) to help inform
nanotechnology and related environmental research programs.

By continuing to actively participate in international scientific fora, EPA will be well

positioned to inform both domestic and international environmental policy. This will provide
essential support for U.S. policy makers who work to negotiate international treaties and trade
regimes. As products made from nanomaterials become more common in domestic and
international channels of trade, policy makers will then be able to rely on EPA for the high
quality science necessary to make effective decisions that could have a significant impact, both
domestically and internationally, on human and environmental health, and economic well-being.

1.5 What EPA is Doing with Respect to Nanotechnology

EPA is actively participating in nanotechnology development and evaluation. Some of
the activities EPA has undertaken include: 1) actively participating in the National
Nanotechnology Initiative, which coordinates nanotechnology research and development across
the federal government, 2) collaborating with scientists internationally in order to share the
growing body of information on nanotechnology, 3) funding nanotechnology research
through EPA’s Science To Achieve Results (STAR) grant program and Small Business
Innovative
Research (SBIR) program and performing in-house research in the Office of Research and
Development, 4) conducting regional nanotechnology research for remediation, 5) initiating the
development of a voluntary program for the evaluation of nanomaterials and reviewing
nanomaterial premanufacture notifications in the Office of Pollution Prevention and Toxics,
6) reviewing nanomaterial registration applications in the Office of Air and Radiation/Office
of Transportation and Air Quality, 7) reviewing potential nanoscale pesticides in the Office
of
Pesticide Programs, 8) investigating the use of nanoscale materials for environmental
remediation in the Office of Solid Waste and Emergency Response; and 9) reviewing
information and analyzing issues on nanotechnology in the Office of Enforcement
and Compliance Assurance.
.

1.5.1 EPA’s Nanotechnology Research Activities

Since 2001, EPA’s ORD STAR grants program has funded 36 research grants nearly 12
million in the applications of nanotechnology to protect the environment, including the
development of: 1) low-cost, rapid, and simplified methods of removing toxic contaminants
from water, 2) new sensors that are more sensitive for measuring pollutants, 3) green
manufacturing of nanomaterials; and 4) more efficient, selective catalysts. Additional
applications projects have been funded through the SBIR program.

In addition, 14 recent STAR program projects focus on studying the possible harmful
effects, or implications, of engineered nanomaterials. EPA has awarded or selected 30 grants
to date in this area, totaling approximately $10 million. The most-recent research solicitations
 2.0 Environmental Benefits of Nanotechnology
2.1 Introduction
As applications of nanotechnology develop over time, they have the potential to help
shrink the human footprint on the environment. This is important, because over the next 50
years the world’s population is expected to grow 50%, global economic activity is expected to
grow 50 0% , and global energy and materials use is expected to grow 30 0% ( World Resources
Institute, 2000). So far, increased levels of production and consumption have offset our gains
in cleaner and more-efficient technologies. This has been true for municipal waste generation,
as well as for environmental impacts associated with vehicle travel, groundwater pollution,
and
agricultural runoff (OECD, 2001). This chapter will describe how nanotechnology can create
materials and products that will not only directly advance our ability to detect, monitor, and
clean-up environmental contaminants, but also help us avoid creating pollution in the first
place. By more effectively using materials and energy throughout a product lifecycle,
nanotechnology may contribute to reducing pollution or energy intensity per unit of economic
output, reducing the “volume effect” described by the OECD.

2.2 Benefits Through Environmental Technology Applications

2.2.1 Remediation/Treatment

Environmental remediation includes the

degradation, sequestration, or other related approaches
that result in reduced risks to human and environmental
receptors posed by chemical and radiological
contaminants such as those found at Comprehensive
Environmental Response, Compensation and Liability
Act (CERCLA), Resource Conservation and Recovery
Act (RCRA), the Oil Pollution Act (OPA) or other
state and local hazardous waste sites. The benefits
from use of nanomaterials for remediation could
include more
rapid or cost-effective cleanup of wastes relative to
current conventional approaches. Such benefits may
derive from the enhanced reactivity, surface area, Figure 13. Nanoscale zero-valent iron
subsurface transport, and/or sequestration encapsulated in an emulsion droplet.
These nanoparticles have been used for
characteristics of nanomaterials.
remdiation of sites contaminated with
Chloro-organics are a major class of variuos organic pollutants. (Image
contaminants at U.S. waste sites, and several cortesy of Dr. Jacqueline W.
Quinn, Kennedy Space Center,
nanomaterials have been applied to aid in their
NASA)
remediation. Zero-valent iron (Fig. 13) has been used
successfully in the past to remediate groundwater by construction of a permeable reactive barrier
(iron wall) of zero-valent iron to intercept and dechlorinate chlorinated hydrocarbons such as
trichloroethylene in groundwater plumes. Laboratory studies indicate that a wider range of
chlorinated hydrocarbons may be dechlorinated using various nanoscale iron particles
in lower material cost as well as reduced weight and power consumption of sensors, leading
to greater applicability and enhanced functionality.

One of the near-term research

products of nanotechnology for
environmental applications is the
development of new and enhanced
sensors to detect biological and
chemical contaminants.
Nanotechnology offers the potential to
improve exposure assessment by
facilitating collection of large
numbers of measurements at a lower
cost and
improved specificity. It soon will be
possible to develop micro- and
nanoscale sensor arrays that can detect
specific sets of harmful agents in the
Figure 14. Piezoresistive cantilever sensor. environment at very low concentrations.
Devices such as these may be used to detect low levels of Provided adequate informatics support,
a wide range of substances, including pollutants, these sensors could be used to monitor
explosives, and biological or chemical warfare agents.
agents in realtime, and the resulting
(Image courtesy
data can be accessed remotely. The
of Dr. Zhiyu Hu and Dr. Thomas Thundat,
Nanoscale Science and Device Group, Oak Ridge
potential also exists to extend these
National small-scale monitoring systems to the
Laboratory) individual level to detect personal
exposures and in vivo distributions of
toxicants. Figure 14 shows an example of a nanoscale sensor.

In the environmental applications field, nanosensor research and development is a

relatively uncharted territory. Much of the new generation nanoscale sensor development is
driven by defense and biomedical fields. These areas possess high-need applications and the
resources required to support exploratory sensor research. On the other hand, the environmental
measurement field is a cost sensitive arena with less available resources for leading-edge
development. Therefore, environmental nanosensor technology likely will evolve by leveraging
the investment in nanosensor research in related fields.

2.3 Benefits through Other Applications that Support Sustainability

Nanotechnology may be able to advance environmental protection by addressing the
long-term sustainability of resources and resource systems. Listed in Table 2 are examples
describing actual and potential applications relating to water, energy, and materials. Some
applications bridge between several resource outcomes. For example, green manufacturing
using nanotechnology (both top down and bottom up) can improve the manufacturing process by
increasing materials and energy efficiency, reducing the need for solvents, and reducing waste
products.
 3.0 Risk Assessment of Nanomaterials
3.1 Introduction
Occupational and environmental exposures to a limited number of engineered
nanomaterials have been reported (Baron et al., 2003; Maynard et al., 2004). Uncertainties in
health and environmental effects associated with exposure to engineered nanomaterials raise
questions about potential risks from such exposures (Dreher, 2004; Swiss Report Reinsurance
Company, 2004; UK Royal Society Report, 2004; European Commission Report, 2004;
European NanoSafe Report 2004; UK Health and Safety Executive, 2004)

EPA’s mission and mandates call for an understanding of the health and environmental
implications of intentionally produced nanomaterials. A challenge in evaluating risk
associated with the manufacture and use of nanomaterials is the diversity and complexity of
the types of
materials available and being developed, as well as the seemingly limitless potential uses of
these materials. A risk assessment is the evaluation of scientific information on the hazardous
properties of environmental agents, the dose-response relationship, and the extent of exposure
of humans or environmental receptors to those agents. The product of the risk assessment is a
statement regarding the probability that humans (populations or individuals) or other
environmental receptors so exposed will be harmed and to what degree (risk characterization).

EPA generally follows the risk assessment paradigm described by the National Academy
of Sciences (NRC, 1983 and 1994), which at this time EPA anticipates to be appropriate for the
assessment of nanomaterials (Figure 15). In addition, nanomaterials should be assessed from a
lifecycle perspective (Figure
16).

Identification

Figure 15. EPA’s Risk Assessment Approach

 Worker Exposure Consumer Exposure

Consume
Raw r End of Life
Consumer
Material Product

Recycle

Industrial emissions Landfills Incinerators

Human Population and Ecological Exposure

Figure 16. Life Cycle Perspective to Risk Assessment

The overall risk assessment approach used by EPA for conventional chemicals is thought
to be generally applicable to nanomaterials. It is important to note that nanomaterials have large
surface areas per unit of volume, as well as novel electronic properties relative to conventional
chemicals. Some of the special properties that make nanomaterials useful are also properties
that may cause some nanomaterials to pose hazards to humans and the environment, under
specific conditions, as discussed below. Furthermore, numerous nanomaterial coatings are
being
developed to enhance performance for intended applications. These coatings may impact the
behavior and effects of the materials, and may or may not be retained in the environment. It
will be necessary to consider these unique properties and issues, and their potential impacts on
fate, exposure, and toxicity, in developing risk assessments for nanomaterials.

A number of authors have reviewed characterization, fate, and toxicological

information for nanomaterials and proposed research strategies for safety evaluation of
nanomaterials
(Morgan, 2005; Holsapple et al., 2005; Blashaw et al., 2005; Tsuji et al., 2006; Borm et al., 2006;
Powers et al., 2006; Thomas and Sayre, 2005). Tsuji et al. (2006) proposed a general framework
for risk assessment of nanomaterials which identified nanomaterial characteristics, such as
particle size, structure/properties,coating, and particle behavior, that are expected be important
in developing nanomaterial risk assessments. These issues are similar to those we note herein.
Other governments have also undertaken efforts to identify research needs for nanomaterial
risk assessment (UK Department for Environment, Food and Rural Affairs, 2005; Borm and
 20 nm 20 nm

(A) (B)
Figure 17. Transmission Electron Microscope (TEM) image of aerosol-generated TiO2
nanoparticles.
(A) Un-aggregated and (2-5 nm) (B) and aggregated (80-120 nm), used in exposure studies to determine
the health impacts of manufactured nanoparticles. Nanoparticle aggregation may play an important role
in health and environmental impacts. (Images courtesy of Vicki Grassian, University of Iowa
[Grassian, et al., unpublished results])

A given nanomaterial can be produced in many cases by several different processes

yielding several derivatives of the same material. For example, single-walled carbon
nanotubes can be produced by several different processes that can generate products with
different
physical-chemical properties (e.g., size, shape, composition) and potentially different ecological
and toxicological properties (Thomas and Sayre, 2005; Oberdörster et al., 2005a). It is not clear
whether existing physical-chemical property test methods are adequate for sufficiently
characterizing various nanomaterials in order to evaluate their hazard and exposure and assess
their risk. It is clear that chemical properties such as boiling point and vapor pressure are
insufficient. Alternative methods for measuring properties of nanomaterials may need to
be developed both quickly and cost effectively.

Because of the current state of development of chemical identification and

characterization, current chemical representation and nomenclature conventions may not be
adequate for some nanomaterials. Nomenclature conventions are important to eliminate
ambiguity when communicating differences between nanomaterials and bulk materials and in
reporting for regulatory purposes. EPA’s OPPT is participating in new and ongoing
workgroup/panel deliberations with the American National Standards Institute (ANSI), the
American Society for Testing and Materials (ASTM), and the International Organization for
Standardization (ISO) concerning the development of terminology and chemical nomenclature
for nanosized substances, and will also continue with its own nomenclature discussions with the
Chemical Abstracts Service (CAS).

3.3 Environmental Fate of Nanomaterials

As more products containing nanomaterials are developed, there is greater potential
for environmental exposure. Potential nanomaterial release sources include direct and/or
indirect
releases to the environment from the manufacture and processing of nanomaterials, releases from
These reactions may alter the physical and chemical properties of nanomaterials and so alter
their behavior in aquatic environments. Certain organic and metallic nanomaterials may possibly
be transformed under anaerobic conditions, such as in aquatic (benthic) sediments. From past
studies, it is known that several types of organic compounds are generally susceptible to
reduction under such conditions. Complexation by natural organic materials such as humic
colloids can facilitate reactions that transform metals in anaerobic sediments (see Nurmi et al.,
2005 and references therein).

In contrast to processes that remove nanoparticles from the water column, some
dispersed insoluble nanoparticles can be stabilized in aquatic environments. For example,
researchers at
Rice University have reported that although C 60 fullerene is initially insoluble in water, it
spontaneously forms aqueous colloids containing nanocrystalline aggregates. The concentration
of nanomaterials in the suspensions can be as high as 100 parts per million (ppm), but is more
typically in the range of 10-50 ppm. The stability of the particles and suspensions is sensitive to
pH and ionic strength (CBEN, 2005; Fortner et al., 2005). Sea surface microlayers consisting
of lipid, carbohydrate and proteinaceous components along with naturally-occurring colloids
made up of humic acids, may have the potential to sorb nanoparticles and transport them in
aquatic
environments over long distances (Moore, 2006, Schwarzenbach et al., 1993).
These interactions will also delay nanoparticle removal from the water column.

Heterogeneous photoreactions on metal

oxide surfaces are increasingly being used as a
method for drinking water, wastewater and
groundwater treatment. Figure 18 shows an
example of the surface of a synthesized metal
oxide nanostructure, Semiconductors such as
titanium dioxide and zinc oxide as nanomaterials
have been shown to effectively catalyze both the
reduction of halogenated chemicals and
oxidation of various other pollutants, and
heterogeneous photocatalysis has been used for
water purification in treatment systems.

Nanoparticle photochemistry is being

Figure 18. Zinc oxide nanostructures studied with respect to its possible application in
synthesized by a vapor-solid process. water treatment. Processes that control transport
(Image courtesy of Prof. Zhong Win Lang and removal of nanoparticles in water and
of Georgia Tech.) wastewater are being studied to understand
nanoparticle fate (Moore, 2006; Wiesner et al.,
2006). The fate of nanosized particles in wastewater treatment plants is not well characterized.
Wastewater may be subjected to many different types of treatment, including physical, chemical
and biological processes, depending on the characteristics of the wastewater, whether the plant
is a publicly owned treatment work or onsite industrial facility, etc. Broadly speaking,
nanosized particles are most likely to be affected by sorption processes (for example in
primary clarifiers) and chemical reaction. The ability of either of these processes to
immobilize or destroy the
particles will depend on the chemical and physical nature of the particle and the residence times
in relevant compartments of the treatment plant. As noted above, sorption, agglomeration
and mobility of mineral colloids are strongly affected by pH; thus pHis another variable that
may affect sorption and settling of nanomaterials. Current research in this area includes the
production of microbial granules that are claimed to remove nanoparticles from simulated
wastewater (Ivanov et al., 2004). Nanomaterials that escape sorption in primary treatment may
be removed from wastewater after biological treatment via settling in the secondary clarifier.
Normally the rate of gravitational settling of particles such as nanomaterials in water is
dependent on particle diameter, and smaller particles settle more slowly. However, settling of
nanomaterials could be enhanced by entrapment in the much larger sludge flocs, removal of
which is the objective of secondary clarifiers.

3.3.4 Biodegradation of Nanomaterials

Biodegradation of nanoparticles may result in their breakdown as typically seen in
biodegradation of organic molecules, or may result in changes in the physical structure or
surface characteristics of the material. The potential for and possible mechanisms of
biodegradation of nanosized particles have just begun to be investigated. As is the case for
other fate processes, the potential for biodegradation will depend strongly on the chemical and
physical nature of the
particle. Many of the nanomaterials in current use are composed of inherently
nonbiodegradable inorganic chemicals, such as ceramics, metals and metal oxides, and are not
expected to
biodegrade. However, a recent preliminary study found that C 60 and C 70 fullerenes were taken
up by wood decay fungi after 12 weeks, suggesting that the fullerene carbon had been
metabolized (Filley et al., 2005). For other nanomaterials biodegradability may be integral to the
material’s design and function. This is the case for some biodegradable polymers being
investigated for use in drug transport (Madan et al., 1997; Brzoska et al., 2004),for
which biodegradability is mostly a function of chemical structure and not particle size.

Biodegradability in waste treatment and the environment may be influenced by a variety

of factors. Recent laboratory studies on C60 fullerenes have indicated the development of
stable colloid structures in water that demonstrate toxicity to bacteria under aerobic and
anaerobic
conditions (CBEN, 2005; Fortner et al., 2005). Further studies are needed to determine whether
fullerenes may be toxic to microorganisms under environmental conditions. One must also
consider the potential of photoreactions and other abiotic processes to alter the
bioavailability and thus biodegradation rates of nanomaterials. In summary, not enough is
known to enable meaningful predictions on the biodegradation of nanomaterials in the
environment and much further testing and research are needed.

3.3.5 Bioavailability and Bioaccumulation of Nanomaterials

Bacteria and living cells can take up nanosized particles, providing the basis for potential
bioaccumulation in the food chain (Biswass and Wu, 2005). Aquatic and marine filter feeders
near the base of the food chain feed on small particles, even particles down to the nanometer
size fraction. The bioavailability of specific nanomaterials in the environment will depend in
part on the particle. Environmental fate processes may be too slow for effective removal of
persistent nanomaterials before they can betaken up by an organism. In the previous section,
it was noted that some physical removal processes, such as gravitational settling, are slower for
nanosized
particles than for microparticles. This would lead to an increased potential for inhalation
exposure to terrestrial organisms and for increased exposure of aquatic organisms to aqueous
colloids. Not enough information has been generated on rates of deposition of nanomaterials
from the atmosphere and surface water, or of sorption to suspended soils and sediments in
the water column, to determine whether these processes could effectively sequester specific
nanoparticles before they are taken up by organisms.

Complexation of metallic nanomaterials may have important interactive effects on

biological availability and photochemical reactivity. For example, the biological availability of
iron depends on its free ion concentrations in water and the free ion concentrations are affected
by complexation. Complexation reduces biological availability by reducing free metal ion
concentrations and dissolved iron is quantitatively complexed by organic ligands. Solar UV
radiation can interact with these processes through photoreactions of the complexes. Further,
iron and iron oxides can participate in enzymatic redox reactions that change the oxidation state,
physical chemical properties and bioavailability of the metal (Reguera et al., 2005).

3.3.6 Potential for Toxic Transformation Products from Nanomaterials

Certain nanomaterials are being designed for release as reactants in the environment,
and therefore are expected to undergo chemical transformation. One example of this is iron
0
(Fe )
nanoparticles employed as reactants for the dechlorination of organic pollutants (Zhang,
2003). As the reaction progresses, theiron is oxidized to iron oxide. Other metal particles are
also
converted to oxides in the presence of air and water. Whether the oxides are more or less toxic
than the free metals depends on the metal. Under the right conditions, certain metal compounds
could be converted to more mobile compounds. In these cases, small particle size would most
likely enhance this inherent reactivity. Some types of quantum dots have been shown to
degrade under photolytic and oxidative conditions, and furthermore, compromise of quantum
dot
coatings can reveal the metalloid core, which may be toxic (Hardman, 2006). Degradation
products from carbon nanomaterials (fullerenes and nanotubes) have not yet been reported.

3.3.7 Interactions Between Nanomaterials and Organic or Inorganic Contaminants:

Effects and the Potential for Practical Applications

The examples cited in this section illustrate how nanomaterials have been demonstrated
to alter the partitioning behavior of chemicals between environmental compartments and
between the environment and living organisms. Furthermore, several nanomaterials are reactive
toward chemicals in the environment, generate reactive species, or catalyze reactions of other
chemicals. These properties are currently understudy for use in waste remediation operations.
It should be noted that the potential also exists for nanomaterials to effect unforseen changes,
if released to the environment in large quantities.

Two types of effects understudy for possible exploitation are sorption and reaction.
The high surface area of nanosized particles provides enhanced ability to sorb both organic and
inorganic chemicals from environmental matrices compared to conventional forms of the same
materials. This property can potentially be utilized to bind pollutants to enhance environmental
remediation. Many examples of immobilized nanomaterials for use in pollution control or
environmental remediation have been described in the literature. These include nanosponges or
nanoporous ceramics, large particulate or bead materials with nanosized pores or crevasses
 Figure 19. SEM of a scanning gate probe.
The large tipis the probe for a scanning tunneling
microscope, and the smaller is a gate that allows
sharper imaging of the sample. Instruments such
as these can be used to analyze nanomaterials.
(Image courtesy of Prof. Leo Kouwehnhoven,
Delft University of Technology. Reprinted
with permission from Gurevich, L., et al.,
2000)
(Copyright 2000, American Institute of Physics.)

3.5 Human Exposures and Their Measurement and Control

As the use of nanomaterials in society increases, it is reasonable to assume that their
presence in environmental media will increase proportionately, with consequences for human
and environmental exposure. Potential human exposures to nanomaterials, or mixtures of
nanomaterials,include workers exposed during the production, use, recycling and disposal of
nanomaterials,general population exposure from releases to the environment as a result of the
production, use, recycling and disposal in the workplace, and direct general population exposure
during the use of commercially available products containing nanomaterials. This section
identifies potential sources, pathways, and routes of exposure, discusses potential means for
mitigating or minimizing worker exposure, describes potential tools and models that may be
used to estimate exposures, and identifies potential data sources for these models.

3.5.1 Exposure to Nanomaterials

The exposure paradigm accounts for a series of events beginning from when external
mechanisms (e.g., releases or handling of chemicals) make a chemical available for absorption
or other mode of entry at the outer body boundary to when the chemical or its metabolite is
delivered to the target organ. Between outer body contact with the chemical and delivery to the
target organ, a chemical is absorbed and distributed. Depending on the nature of the chemical
and the route of exposure, the chemical may be metabolized. For the purposes of this section,
we will limit the discussion to the types of resources that are needed (and available) to assess
exposure up to the point where it is distributed to the target organ.

3.5.2 Populations and Sources of Exposure

The potential for intentionally produced nanomaterials to be released into the
environment or used in quantities that raise human exposure concerns are numerous given their
also occur (such as through the activities of the mucocilliary escalator). The quantity ingested
is anticipated to be relatively small in terms of mass.

3.5.3.3 Dermal Exposure

Dermal exposure to nanomaterials has received much attention, perhaps due to concerns
with occupational exposure and the introduction of nanomaterials such as nanosized titanium
dioxide into cosmetic and drug products. One reference study was found to have investigated
issues involved with potential dermal exposure to a SWCNT material. The study suggests that
more research will be needed in this area. This study noted that airborne particles of SWCNT
may contribute to potential dermal exposure along with surface deposits due to material
handling. Surface deposits on gloves were estimated to be between 0.2 mg and 6 mg per
hand. (Maynard et al., 2004)

There is an ongoing debate over the potential for penetration through “healthy/intact”
versus damaged skin. Hart (2004) highlights physiological characteristics of the skin that may
permit the absorption of nanosized materials. In particular the review highlights a
conceivable route for the absorption of nanoparticles as being through interstices formed by
stacking and
layering of the calloused cells of the toplayer of skin (Hart, 2004). Movement through these
interstices will subsequently lead to the skin beneath, from which substances can be absorbed
into the blood stream. Nanomaterials also have a greater risk of being absorbed through the
skin than macro-sized particles (Tinkle, 2003). Reports of toxicity to human epidermal
keratinocytes in culture following exposure to carbon nanotubes have been made (Shvedova et
al., 2003;
Monteiro-Riviere et al., 2005). A significant amount of intradermally injected nanoscale
quantum dots were found to disperse into the surrounding viable subcutis and to draining lymph
nodes via subcutaneous lymphatics (Roberts, D.W. et al., 2005). It has recently been reported
that quantum dots with different physicochemical properties (size, shapes, coatings) penetrated
the stratum corneum and localized within the epidermal and dermal layers of intact porcine skin
within a maximum 24 hours of exposure ( Ryman- Rasmussen et al. , 2 00 6 ). Drug delivery
studies using model wax nanoparticles have provided evidence that nanoparticle surface charge
alters
blood-brain barrier integrity and permeability (Lockman et al., 2004).

3.5.3.4 Ocular Exposure

Ocular exposure to nanomaterials has received little attention. However, the potential for
ocular exposure to nanomaterials from deposition of airborne powders or mists in the eyes or
from splashing of liquids must also be considered.

3.5.4 Exposure Mitigation

Approaches exist to mitigate exposure to fine and ultrafine particulates. Some
approaches such as engineering controls are applicable to the workplace and may mitigate
environmental releases while others such as personal protective equipment (PPE) are primarily
applicable to the workplace. NIOSH suggests considering the range of control technologies and
personal protective equipment demonstrated to be effective with other fine and ultrafine
particles (NIOSH, 2005a). In the hierarchy of exposure reduction methods, engineering controls
are
preferred over PPE.
3.5.4.1 Engineering Controls

Engineering controls, and particularly those used for aerosol control, should generally be
effective for controlling exposures to airborne nanoscale materials (NIOSH, 2005a). Depending
on particle size, nanoparticles may diffuse rapidly and readily find leakage paths in engineering
control systems in which containment is not complete (Aitken et al., 2004). However, a well-
designed exhaust ventilation system with a high efficiency particulate air (HEPA) filter should
effectively remove nanoparticles (Hinds, 1999). As with all filters, the filter must be properly
seated to prevent nanoparticles from bypassing the filter, decreasing the filter efficiency
(NIOSH, 2003). Aitken et al. (2004) recommends that engineering controls (e.g., enclosures,
local exhaust ventilation, fume hoods) used to control exposure to nanoparticles need to be of
similar quality and specification as those typically used for gases. However, the report also notes
that no research has been identified evaluating the effectiveness of engineering controls for
nanoparticles.

Efficient ultrafine particle control devices (e.g., soft x-ray enhanced electrostatic
precipitation systems) may have applicability to nanoparticles control (Kulkarni et al., 2002).
HEPA filters may be effective, and validation of their effectiveness is currently being
studied (NIOSH, 2005a). Magnetic filter systems in welding processes have proven effective
in
capturing magnetic oxides and the use of nanostructured sorbents in smelter exhausts to
prepare ferroelectric materials may also have applicability (Biswas et al., 1998).

3.5.4.2 Personal Protective Equipment (PPE)

Properly fitted respirators with a HEPA filter may be effective at removing
nanomaterials. Contrary to intuition, fibrous filters trap smaller and larger particles more
effectively than mid-sized particles. Small particles (<100 nm) tend to make random Brownian
motions due to their interaction with gas molecules. The increased motion causes the particle to
“zig-zag around” and have a greater chance of hitting and sticking to the fiber filter (Luther,
2004). Intermediate-sized particles (>80 nm and < 2000 nm) can remain suspended in air for the
longest time. (Bidleman, 1988; Preining, 1998; Spurny, 1998; Atkinson, 2000; UK Royal
Society, 2004; Dennenkamp et al., 2002)

NIOSH certifies particulate respirators by challenging them with sodium chloride (NaCl)
aerosols with a count median diameter 75 nm or dioctyl phthalate (DOP) aerosols with a count
median diameter of 185 nm [42 CFR Part 84.181(g)], which have been found to be in the most
penetrating particle size range (Stevens and Moyer, 1989). However, as with all respirators, the
greatest factor in determining their effectiveness is not penetration through the filter, but rather
the face-seal leakage bypassing the device. Due to size and mobility of nanomaterials in the air,
leakage may be more prevalent although no more than expected for a gas (Aitken, 2004). Only
limited data on face-seal leakage has been identified. Work done by researchers at the U.S.
Army RDECOM on a headform showed that mask leakage (i.e., simulated respirator fit factor)
measured using submicron aerosol challenges (0.72 µm polystyrene latex spheres) was
representative of vapor challenges such as sulfur hexafluoride (SF6) and isoamyl acetate
(IAA) (Gardner et al., 2004).