Environmental Applications of Nanotechnology:

Going Green
October 6, 2010
The concept of Green Nano is our ability to design industrial
processes and everyday products with the protection of human
health and the environment in the forefront of the design phase. It
describes the development of products that have environmental
applications. This webinar will address how to design "green"
products and showcase technologies that show promise for
environmentally beneficial applications, such as environmental
clean up, water purification, and energy efficiency. Hear from two
leading experts in the area of Green Nano and find out how
integration of these approaches can benefit your business.

Environmental Applications of Nanotechnology:

Going Green

Program

1. Welcome
2. Introductions
3. Presentations
4. Question and Answer Session
5. Conclusion

1
 A Preliminary Word
These presentations provide information about the law. Legal
information is not the same as legal advice, which involves the
application of law to an individual's specific circumstances. The
interpretation and application of the law to an individual’s specific
circumstance depend on many factors. These presentations are
not intended to provide legal advice.

The information provided in these presentations is drawn entirely

from publicly available information. The views expressed in this
presentation are the presenter's alone and not those of the
presenter's clients or constituents.

Environmental Applications of Nanotechnology:

Going Green
Webinar Sponsor and Host

NanoReg
NanoReg is a professional services firm, specializing in nanotechnology regulatory compliance,
strategic planning, association management, workshops, and training programs. NanoReg
publishes the NanoReg Report, providing current information on government regulations and
EHS issues related to the development, production and use of nanoscale materials.

John DiLoreto is the founder of NanoReg. Mr. DiLoreto is the

publisher of the NanoReg Report and Executive Director of the
SOCMA Nanotechnology Coalition
Email: johnd@nanoreg.net
Phone: 301-987-0924

2
Environmental Applications of Nanotechnology:
Going Green
Webinar Sponsor and Host
Keller and Heckman LLP
Global regulatory compliance is essential in today’s multinational corporate environment.
Keller and Heckman LLP, founded in 1962, is adept at interdisciplinary approaches to
problem-solving, with an in-house scientific staff that works closely with the firm's
attorneys on matters of technical complexity. Many of our attorneys also have
government experience and expertise in multiple areas of the law.

Martha Marrapese joined Keller and Heckman in 1992. Ms. Marrapese

focuses on emerging technologies in the industrial chemicals, antimicrobial
pesticides, and food packaging sectors. Ms. Marrapese facilitates the
registration of new technologies in the global economy with a particular
emphasis on polymer, biotechnology, and nanotechnology applications.
Email: marrapese@khlaw.com
Phone: 202-434-4123

Webinar Presenters
Dr. Bettye L. (Smith) Maddux, Assistant Director
Safer Nanomaterials and Nanomanufacturing Initiative (SNNI)
Dr. Maddux is conference chair and organizer of the Greener Nano
Conference series and serves on the Pacific Northwest National Laboratory's
EMSL Peer Review Proposal Committee. She also serves as an expert for the
International Standards Organization (ISO) Technical Committee 229 for
Nanotechnologies. She has published over 40 peer-reviewed research articles,
a book chapter, policy-related reports and invited articles in the fields of
nanotechnology, biophysics, biochemistry, materials science, and chemical
carcinogenesis.
Email: bmaddux@uoregon.edu Phone: (541) 713 1330

Dr. Olga Koper, Chief Technology Officer, NanoScale Corporation

Dr. Koper has authored and co-authored over 30 papers and co-holds 25
patents for composition and applications of nanomaterials. She has
considerable experience in the synthesis and optimization of novel reactive
nanomaterials for chemical and bio-related applications and co-developed
nanocrystalline metal oxides that are utilized in consumer and military
applications, including environmental remediation, odor control and even
destruction of chemical and biological warfare agents.
Email: OKoper@NanoScaleCorporation.com Phone: (785) 537-0179 x103

3
 Greening Nanotechnology:
reducing principles to practice

Dr. Bettye L.S. Maddux

Oregon Nanoscience and Microtechnologies Institute
(ONAMI)
Safer Nanomaterials and Nanomanufacturing Initiative
(SNNI)
Materials Science Institute, University of Oregon
(UO)

Outline

• Brief introduction to ONAMI and SNNI

• Applications and implications of nanotechnology
• Principles of green chemistry
• Applying these principles to nanoscience and
nanotechnology
• Reducing principles to practice
• Benefits of going green

4
 Oregon Nanoscience and Microtechnologies Institute

discover * develop * deploy

Collaborative Research User facilities Commercialization

ONAMI is focusing on five Northwest Nanonet™
research ONAMI’s shared user ONAMI’s “Gap” grants support
thrusts selected for their synergy facilities and consultants are Oregon companies as they cross
with global challenges and available to universities, the chasm between technology
regional industry, research and government and industry to development and product
commercialization potential. advance research and introduction.
development.
•Microtechnology Based Energy
and Chemical Systems •Materials Characterization
•Greener Nanomaterials and
SNNI •Prototyping and Fabrication
Nanomanufacturing
•Industrial Partnerships
•Solution-Processed Inorganic
Films for Printed and Flexible
Electronics
•Nanoscale Metrology and
Nanoelectronics
•Nanomedicine and
Nanobiotechnology

http://www.onami.us/

Safer Nanomaterials and Nanomanufacturing Initiative (SNNI)

• An ONAMI research program at University of Oregon
• Research: high performance, economical nanomaterials that
pose minimal harm to health or the environment
• Merges green chemistry and nanoscience to produce
• Greener nanomaterials
• More efficient, safer nanomanufacturing processes
• Nine Teams (14 research projects) ~ 25 Sr.
Researchers/faculty (chemists, biologists, toxicologists,
physicists, materials scientists and engineers from OSU,
PSU, UO and PNNL)
• In 5th year of funding (from the Air Force Research
Laboratory) - 6th year budget in process

www.greennano.org

5
 Research Thrusts at SNNI
Dr. Jim Hutchison (Chemistry and MSI, UO), founding Director

Greener Nanomanufacturing
Designing Safer Nanomaterials
of Engineered Nanoparticles

Nanodevice applications for energy

and energy storage

• 9 interdisciplinary teams
• ~$8 M/yr external funding
from PIs
• >100 peer-reviewed
publications

SNNI’s Greener Nano Research Strategy

Iterative research strategy FUND interdisciplinary teams
Nanoscience
Chemistry
Physics
“design rules” Biology
for
nanomaterials
Toxicology
A variety of engineers
Nanoscale metrology

Nano-Bio Interactions Knowledgebase

Overarching goals
Fundamental science
Guiding principles for design
Solutions to enhance innovation
Strategic partnerships for
commercialization and outreach

6
 Applications: the promise of nanotechnology to society

• Clean energy (e.g solar)

http://www.cosmosmagazine.com/node/1721
• High performance energy storage
• Clean drinking water for everyone
• Medical diagnostics and therapies
• Stronger, lighter materials
• Sensors
• Smaller, faster devices (computers,
phones…)
• Clean, sustainable chemical production

Implications of nanotechnology: unknown risks

From the Lloyd’s Emerging Risks Team

Report (Dec 2007)

• Nanoparticles, different material properties

• Potential benefits - positive effects
• Unknown health impacts
• Unknown environmental impacts
• Lack of regulation

“Currently almost all regulation of “When stakeholders (producers,

nanotechnology is done using existing
mechanisms. Stakeholders in
nanotechnology are divided on
whether specific regulation is
required.” (Lloyd’s, 2007)
government and the public) are out
and of sync, regulatory steps by state
and federal officials are to be
expected.” (John DiLoreto,
Nanotechnology Now, 2010)

7
 The relationship between applications and implications

Traditional research activities focused on discovery of new applications

Pioneering Nanotech
Applications

Research on EHS implications developed in parallel but separate from applications

Nano EHS
Implications

Applications research EHS implications research

J. Hutchison, ACS Nano 2008, 2, 395-402

Pioneering applications
Innovation and invention - clearly a societal benefit.

8
 But at some cost to health and the environment

“Industrial chemistry has historically relied on the criteria of performance and cost.”

“We’ve been living with warning about industrially synthesized and dispersed
chemicals for decades now. But we’ve responded to these concerns on a piecemeal,
substance-by-substance basis, taking one material off the market when its adverse
effect have been recognized and substituting another without altering the framework
of this process.”
(from “Chasing Molecules, Poison Products, Human Health and the Promise of Green Chemistry” 2009 by E. Grossman)

“He Who Forgets the Past is Doomed to

Repeat It”
- John DiLoreto - 2010 Nanotechnology Now article

The relationship between applications and implications

Making a concerted effort to learn from the past.

Traditional research activities focused on discovery of new applications

Pioneering Nanotech
Applications

Research on EHS implications developed in parallel but separate from applications

Nano EHS
Implications

Of the many nano EHS studies to date,

what have we learned from them?

J. Hutchison, ACS Nano 2008, 2, 395-402

9
Despite many EHS studies, there is still no real consensus

“The peer-reviewed literature contains thousands of articles

documenting results from [toxicology] tests, all conducted in an effort
to determine the health and safety of nanomaterials. Yet the
scientific community has yet to determine which nanomaterials are
hazardous to the environment or humans…” Lubick, ES&T, March 2008

Why? Complex materials, purity, dose, lack of experimental standardization

Bridging the gap

Pioneering Nanotech Pioneering Nanotech

Applications Applications

Coordinated effort

Nano EHS Nano EHS

Implications Implications

A strong bridge between applications and implications will enable us to

anticipate new problems and develop proactive solutions

Risk = ƒ(Hazard, Exposure)

J. Hutchison, ACS Nano 2008, 2, 395-402

10
 Green Chemistry: the route to safer design,
production and application

Green chemistry is the utilization of a set of principles that reduces or

eliminates the use or generation of hazardous substances in the design,
manufacture and application of chemical products
– PT. Anastas, J.C. Warner

Focus on design by reducing hazard rather than controlling exposure Æ

inherent safety
Risk = ƒ(Hazard, Exposure)
Effect on Applications and Implications:
•Advances applications
•Reduces implications

In virtually every aspect in society, it has long been

acknowledged that preventing a problem is superior
to trying to solve it once its been created.
– Paul Anastas and John Warner, 2000

The 12 Principles of Green Chemistry

1. Prevent Waste
2. Maximize Atom Economy
3. Design less Hazardous Chemical
Synthesis
4. Design Safer Chemicals and Products
5. Use Safer Solvents/Reaction Conditions
6. Increase Energy Efficiency
7. Use Renewable Feedstocks
8. Avoid Chemical Derivatives
9. Use Catalysts
10. Design for Degradation
11. Analyze in Real-Time to Prevent Pollution
12. Minimize the Potential for Accidents
Published in 1998
Solvents/catalysts/energy/rea
ction steps, etc
A(Reactant) + B(Reactant) Æ Æ Æ P(Product) + W(waste)

11
 Traditional pharmaceutical production
For every pound of active drug, ~ 200 pounds of waste is generated
From: An Executive Guide to Pharmaceutical Manufacturing Efficiency and the Effect of Environmental Legislation
http://tinyurl.com/33wca4u

“Pharmaceutical production is often cited as one of the most

wasteful sectors in the chemical industry," says Shannon Stahl
http://insciences.org/article.php?article_id=9173

+ = ?

Zoloft: A green chemistry example

Action
•Changed the catalyst
•Cut reaction from 3 steps to 1 step
•Replaced 4 solvents (methylene chloride,
tetrahydrafuran, toluene, hexane) with 1 - ethanol Sertraline (Zoloft)
Results
•Eliminated annual waste per pound:
• 310,000 lbs, titanium tetrachloride
• 220,000 lbs, 50% sodium hydroxide
• 330,000 lbs, 35% hydrochloric acid waste
• 970,000 lbs, solid titanium dioxide
•Doubled product yield and significantly reduced
EHS impact
•Won the U.S. EPA’s 2002 Presidential Green
Chemistry Award for applying Green Chemistry to
the manufacturing of Zoloft

12
 Going green is good for business

Pfizer is not alone in turning to green chemistry. ACS GCI

Pharmaceutical
roundtable
“Pharma goes green to cut costs”
(14 companies
Royal Society of Chemistry, 09 July 2008 participate)

Going green is cost beneficial: it just has the

perception that it is more expensive to do.

“In every case I know, the green option is the low cost
option.” – David Constable
http://www.rsc.org/chemistryworld/News/2008/July/09070801.asp

Green
Green chemistry
chemistry works
works for
for an
an established
established industry,
industry,
what
what about
about an
an emerging
emerging technology?
technology?

Nanotechnology: an emerging technology

>1000 products in the PEN database
http://www.nanotechproject.org/inventories/

Air Oasis!
Air Purifier Pentel Aromatic pens Nano care Technologies
nano scented … designed to Antibacterial tableware &
satisfy your poetic urges kitchen tools
Strom Fishing Lures

Demron™
radiation protection fabric for
individuals … better heat
dissipation

Stealth CNT® Baseball Bat

Dockers Lancome® Nanofilms
Rénergie®
Microlift
Fusion™
Technology
(hearing aids)
Skybright
Natural Health

13
 Applying the principles of green chemistry to nanoscience

Opportunity to:
• innovate and apply nanotechnology in
unique applications
• reduce costs for production of
nanomaterials
• “get it right” the first time, rather than
clean up later
• win public support McKenzie, L.C; Hutchison, J.E. “Green
nanoscience,” Chemistry Today, 2004,
30-33.

How do we apply the principles of green chemistry to nanoscience?

nanoscience?

Greener nanomaterials and

Green Chemistry Principles production methods
or
P1: Prevent waste nf
P2: Atom economy esig safer nanomaterials
D P4, P12
P3: Less hazardous chemical synthesis
P4: Designing safer chemicals reduced environmental impact
P5: Safer solvents/reaction media P7, P10
P6: Design for energy efficiency
P7: Renewable feedstocks waste reduction
P8: Reduce derivatives P1, P5, P8
P9: Catalysis
P10: Design for degradation/end-of-life process safety
P3, P5, P7, P12
P11: Real-time monitoring and process
control materials efficiency
P12: Inherently safer chemistry P2, P5, P9, P11
(minimize accidents)
energy efficiency
tas & Warner “Green Chemistry: Theory and Practice”, P6, P9, P11
1998, Oxford University Press

Dahl, Maddux, Hutchison, “Toward Greener

Nanosynthesis”, Chem. Rev, 2007, 107:
2228-69

14
 Design for waste production

Greener syntheses and purification - nanoparticles

Develop selective nanosyntheses
Design
Design for
for waste
waste
Eliminate solvent-intensive purifications reduction
reduction
Develop new purification methods, e.g. (P1,P5,P8)
(P1,P5,P8)
nanofiltration

Adapted from Dahl, J.A.; Maddux, B. L. S.; Hutchison, J.

E. “Toward Greener Nanosynthesis,” Chem. Rev.2007,
107, 2228.

Greener synthesis of functionalized gold nanoparticles

AuCl(PPh3)
B2H6 PPh3
ethanol
C6H6
Ph3P
Cl PPh3
NaBH4 (10 eq)
HAuCl4 + PPh3
toluene/water/TOABr (1 eq) Au-TPP
Cl
PPh3
Using the new method: Cl PPh
Ph3P 3
Safer, easier, faster preparation
Narrow dispersity
Cheaper (~ $500/g vs. “$300,000/g”) (d = 1.5 +/- 0.4 nm)
Eliminates use of diborane and benzene

Weare, Reed, Warner, Hutchison J. Am. Chem. Soc. 2000, 122,

12890.
Hutchison, et al. Inorg. Syn. 2004, 34, 228.
US Patent # 6,730,537: Issued May 4, 2004.

15
 Greener purification of nanoparticles

Diafiltration reduces solvent

consumption and provides cleaner,
well-defined building blocks Purity affects NP toxicity and
performance
Nanomaterials purification
Traditional:
15L solvent per gram NP
3 days work

Diafiltration:
No organic solvent (eliminates >
10,000 pounds/pound NPs )
15 minutes work

Sweeney, Woehrle, Hutchison

J. Am. Chem. Soc. 2006, 128, 3190.

A diverse library of functionalized nanoparticles

R= -(CH2)17CH3 -(CH2)2SO3-Na+ -CH2COO-Na+

-(CH2)15CH3 -(CH2)3SO3-Na+ -(CH2)2COOH

-(CH2)11CH3 -(CH2)2N+HMe2Cl- -(CH2)11COOH

-(CH2)9CH3 -(CH2)2N+Me3Cl- -(CH2)2OH

-(CH2)8CH3 -(CH2)2O(CH2)2N+Me3-OTs -(CH2)2PO(OH)2

-(CH2)7CH3 -(CH2)2O(CH2) 2O(CH2)2 N+Me3- -[(CH2)2O]2(CH2)2OH

OTs -(CH2)2O(CH2)2OH
-(CH2)5CH3
-(CH2)2O(CH2) 2O(CH2)2 N+Et3-OTs -[(CH2)2O]2CH2COOH
-(CH2)2CH3
-(CH2)2Si(OMe)3 -(CH2)2COGlyGlyOH
-
Core d = (CH2)2CONH(CH2)14CH3
0.8-nm,
1.5-nm,
Characterization
10 nm
TEM - size and dispersity
UV/vis - crude size, aggregation
NMR - small molecule contamination
TGA - ligand/core ratio
XPS or EA - elemental composition

J. Am. Chem. Soc. 2005, 127, 2172 and Inorg. Chem. 2005, 44, 6149

16
 Safer design of nanomaterials

Avoid incorporation of toxic elements

Determine biological impacts Design
Design of
of safer
safer
nanomaterials
nanomaterials
Use SARs to design effective, safer
(P4,P12)
(P4,P12)
materials that possess desired physical
properties

Adapted from Dahl, J.A.; Maddux, B. L. S.; Hutchison, J.

E.“Toward Greener Nanosynthesis,” Chem. Rev.2007,
107, 2228.

Assessing the biological impacts

Tier 1: Toxicity Screening

Toxicity testing in cells, tissues and whole
organisms
• In vitro (human cell, invertebrate tissue
cultures)
• In vivo (vertebrate and invertebrate
models)
Tier 2: Cellular Targets and Distribution
Defined in vivo
eye
• Fluorescent nanomaterials
heart
• Targeted assays
Tier 3: Molecular Expression
Genomic Responses
• Whole animal gene expression profiles

Structure Activity Relationships

Feed data back into design scheme

17
 Screening toxicity and establishing the design rules
Gold Cores
Library of well-defined
nanoparticles

Surface Functionalization

Tier 1 screening
Neutral: 2-(2-mercaptoethoxy)ethanol (MEE)

S.L. Harper et al,

Manuscript submitted

Neutral: 2,2,2-[mercaptoethoxy(ethoxy)]ethanol (MEEE)

Anionic: 2-mercaptoethanesulfonate (MES)

Cationic: N,N,N-trimethylammoniumethanethiol (TMAT)

Observed differential toxic response based on size and charge

An iterative approach to designing greener nanoparticles

Nanomaterial-
Biological Interactions Knowledgebase

18
 Despite many
EHS studies,
Making sense of the EHS data
there is still no
real consensus

http://nbi.oregonstate.edu/

9 To serve as a repository for annotated data on the physicochemical

properties of nanomaterials and their biological interactions
9 To organize and analyze data and compare results across research
platforms in an effort to define robust structure-activity relationships
9 To identify the functional design principles of high performing,
environmentally-benign nanomaterials
9 To predict potential biological impacts of unsynthesized nanomaterials

Nanoinformatics 2010
3-5 November, Arlington, VA
http://nanotechinformatics.org/

Dr. Stacey Harper, OSU

Reducing principles to practice

Functionalized nanoparticles

Diagnostic/Sensin
Antimicrobials g

Biomolecular Therapeutics
Optical materials
nanolithography

50 nm

Dr. Jim Hutchison, UO

19
 Reducing principles to practice
Nanostructured solids for high-efficiency energy production and storage

Inorganic lithography Inorganic imprinting

>20nm, highest fidelity, Direct low-temperature
written with e-beam imprinting

Display and PV materials from aqueous inks

http://pages.uoregon.edu/grnchem/
Dr. Doug Keszler, OSU

Merging green chemistry and nanoscience

“G
re
en
Na
no

Provides opportunities to
sc

develop cleaner nanomaterials

ie
nc
e”

Design - environmentally benign

nanomaterials with tunable properties
Manufacture - complex
nanomaterials efficiently, minimizing
hazardous substances
Assemble/interface - nanomaterials
using a bottoms-up approach,
reducing waste

McKenzie, L.C; Hutchison, J.E.

“Green nanoscience” Chemistry
Today, 2004, 30-33.

20
 Green chemistry is guiding greener nanotechnologies

PPh3

Ph3P
Cl PPh3

Au-TPP
Cl
PPh3
Cl PPh
Ph3P 3

Synthesis/pr Purification/anal Testing Nanomaterial

oduction ysis strategies design

Benefits:
• provide tools for smart product and process design
• spur innovation through exploration of new materials and properties
• enable commercialization by reducing uncertainty
• enhance transparency for the public
• provide a framework for subsequent technologies and improved product
safety and stewardship

The bottom line

For more information:

http://www.greennano.org/

21
 Environmental
Applications of
Nanomaterials
Olga B. Koper, Ph.D.
NanoScale Corporation

NanoScale Corporation
• Kansas State University spin-off
• Proven clean technology; existing products and Customers
• Contract R&D for DoD, DoE, EPA, NIH, NSF, USDA
• Collaborations with universities, federal laboratories, commercial
institutes, private and public companies
• Large Volume Production, ISO 9001 Certified
• Strong IP (25 U.S. and 20 international patents issued, 18 trademarks)
• Commercialization Successes (i.e., U.S. DoD – M295, ServiceMaster)

FAST-ACT® OdorKlenz-Air™ ChemKlenz® Energy (44)

Decontamination Environment & Air Quality Chemical Safety Scrubbing & Alternative Fuels

22
NanoScale Environmental
Products

OdorKlenz for
CDW

2002 2009

1998 2008 2010

SpillKlenz M295
Decontamination Kit

(45)

Outline

• Market Size
• Environmental remediation
• Applications of
nanotechnology: air, water and
soil
– Reactive
– Adsorptive
• Other environment related
applications
(46)

23
 Market Size for Environmental
Nanotechnology (“E-nano”)
• The global market for nanotechnology in environmental
applications generated $1.1B in 2008 (est. $2B 2009)
and is expected to increase at a compound annual
growth rate (CAGR) of 61.8% to reach $21.8B in 2014
• The largest market share: environmental protection
segment, $661.4 million in 2008. This is expected to
increase to $10.3 billion in 2014, for a CAGR of 58.1%
• Second: environmental enhancement with $189.4
million in 2008 and reaching $2.8 billion in 2014, for a
CAGR of 43.6%

(47)
Source: BCC Research , Report NAN039B, July 2009

Global Environmental Nano Markets

for Air, Water, and Soil
12,000

10,000

8000
$ Millions

6000

4000

2000

0
2008 2009 2014

Protection Maintenance Enhancement Remediation

(48)
Source: BCC Research , Report NAN039B, July 2009

24
Environmental Applications
• Prevention: environmentally benign sustainable products,
green manufacturing, nano based filters
• Detection and monitoring of environmental agents, i.e.,
rapid and accurate mapping of site contamination,
detecting pipeline leaks, smaller sizes of detectors for
portable field devices
• Protection from and remediation of materials
contaminated with hazardous substances: air, water and
soil
- In-situ vs. ex-situ treatment
- Removal/adsorption vs. destruction
(49)

Advantages of Nanomaterials

• Large surface to volume ratio: faster kinetics, increased

contact with contaminants
• Higher density of active sites on the surface
• Higher intrinsic reactivity
• Higher mobility: capability of deep underground penetration
• Formation of stable suspension for ground water treatment
• Effectiveness for broad range of contaminants
• More benign by-products
• Remediation through chemical reaction and catalysis

(50)

25
 Environmental Remediation

• ~$1 billion for remediation projects allocated to the EPA in

the American Recovery and Reinvestment Act (2009)
• 1,255 sites on National Priorities List (NPL) (>80% have
groundwater contamination)
• Main contaminants: solvents and other organics, metals,
and petroleum products
• Ex-situ processes: pump-and-treat
• In-situ processes: permeable reactive barriers, thermal
treatment, chemical oxidation, surfactant cosolvent
flushing, bioremediation
(51)

Environmental Remediation
• Desired Outcome: reduce the overall costs as compared to
current approaches, cleanup time, eliminate the need for
treatment and disposal of contaminated soil, and reduce
some contaminant concentrations to near zero
• EPA predicts that nanoremediation can save $87 billion to
$98 billion in cleaning up U.S. hazardous waste sites over
the next 30 years

(52)

26
Nanoremediation

(53)
Source: Karn, et. al. Environmental Health Perspectives, 117 (112), 12/09

Promising Nanomaterials for

Active Remediation

• Zero-Valent metals, i.e., nano iron (nZVI)

• Bimetallic nanoparticles (Pd/Fe)
• Nanoparticle metal oxides (reactive TiO2, MgO)
• Photocatalytic TiO2, self-cleaning surfaces

(54)

27
 Potential efficacy of nano iron
towards contaminants
• Chlorinated methanes, i.e., carbon tetrachloride
• Trihalomethanes, i.e., bromoform
• Chlorinated ethenes, i.e., tetrachloroethylene
• Chlorinated benzenes, i.e., tetrachlorobenzene
• Other polychlorinated hydrocabons, i.e., PCBs, dioxins
• Pesticides, i.e., DDT, Lindane
• Organic dyes, i.e., orange red
• Other organic contaminants, i.e., TNT
• Heavy metal ions, i.e., mercury, nickel, silver, cadmium
• Inorganic ions, i.e., dichromate, arsenic, perchlorate, nitrate

More than 40 pilot and full-scale applications of metal nanoparticles

have been carried out worldwide since 2001: oil fields, manufacturing
sites, military installations, private properties, and residences

(55)
Source: Wei-xian Zhang, Journal of Nanoparticle Research 5: 323–332, 2003, and EPA Reports.

In-situ Remediation with Nano Iron

TCE + Fe0 → Hydrocarbon products + Cl– + Fe2+/Fe3+

(56)
Source: Wei-xian Zhang, Journal of Nanoparticle Research 5: 323–332, 2003.

28
Rate constants for reduction of CCl4
by nZVI and two larger Fe0

Nano iron provides 2

orders of magnitude
increase in the rate
constant (per mass)

Source: P. Tratnyek, Nanotoday 05/2006

(57)

Spill/Vapor Remediation
FAST-ACT® (NanoScale): a chemical containment and
neutralization system that first responders can use to
clean up toxic chemical releases of industrial chemicals
or chemical warfare agents

(58)
Source: NanoScale Corporation

29
First Applied Sorbent Treatment
Against Chemical Threats
• Effective against a broad range of
toxic chemicals and chemical
warfare agents
• Capable of neutralizing liquid and
vapor hazards
• Non-toxic, non-flammable and non-
corrosive
• Applicable to any spill
• Effective over a broad range of
environmental conditions
• Easy to use

(59)

Promising Nanomaterials for

Adsorptive Remediation

• Self-assembled monolayers on mesoporous supports

(SAMMSTM)
• Dendrimers
• Swellable (up to 8 times) organically modified silica
(SOMS) – ABSMaterials, Inc.; for capture of neat,
dissolved, or vapor-phase organics from water
• Nanotubes: carbon, metal oxides
• Metalloporphyrinogens: complexes of metals with
naturally occurring, organic porphyrins

(60)

30
 Self-assembled Monolayers on
Mesoporous Supports (SAMMSTM)
• Nanoporous ceramic substrate coated with a monolayer of
functional groups tailored to preferentially bind to the target
contaminant
• Developer: the Pacific Northwest National Laboratory and
Steward Environmental Solutions
• Applications: remediation, water treatment (removal of
mercury, chromate, arsenate, pertechnetate, and selenite),
catalyst, sensor and controlled-release markets
• Fast kinetics, high material loading, and
excellent selectivity
• Field demonstration: removal of mercury
from lab waste, EVS scrubber waste and oil
(61)

Dendritic Polymers
• Hyper-branched, well-organized polymer molecules with
three components: core, branches, and end groups
• Dendrimer surfaces can be modified to enhance specific
chemical activity
• Used for air, water and soil in situ or ex situ
- Removal of Cu(II) from water
- Soil washing to remove Pb(II) contamination

(62)

31
 Oil Spill Remediation
MIT: a “paper towel” for oil spills that is comprised of a
membrane or mat of potassium manganese nanowires.
The oil can be recovered by heating the mat, which can
then be reused.

(63)
Source: Nature Nanotechnology

Water Remediation Methods

Applications: industrial, commercial, residential, and personal

•Mechanical: filtration through an inert medium, i.e.,
membranes, sand; settling ponds
•Chemical: chlorination/bromination; adsorption and or
destruction: activated carbon, metal oxides; photocatalysis
•Biological: use of microorganisms to decompose undesired
compounds

Nanotechnology can have an impact in all these areas

(64)

32
 Nanotechnology for Water
Filtration
Approaches: nanosorbents, nanocatalysts, bioactive
nanoparticles, nanostructured catalytic membranes, and
nanoparticle enhanced filtration
•Biological species: nanofiltration with nano zinc oxide,
copper oxide, aluminum oxide, titanium oxide (0.1-10% wt.),
silver coated filters
•Organic and inorganic compounds: nano doped activated
carbon, nanometals, nanotubes, nanometal oxides,
photocatalytic TiO2
•Heavy metals: activated carbon iron impregnated sorbent,
iron hydroxide on aluminum oxide, photocatalytic TiO2

(65)

Nanotechnology for Air Filtration

• Nanofibers: electrospun cellulose, polymeric ,
spider silk, nanotube, nanocrystalline polymers,
biopolymers, nanometric pores, nonwoven
fabrics, enzyme nanoparticles, etc.
• Membranes: nanoporous, nanoparticle enhanced,
carbonaceous adsorptive, reactive, zeolites,
aerogel, hybrid, nanotube, dendrimers, etc.
• Packed bed: nanometal oxides, nano doped
carbons
• Nano HVAC enhanced: metal oxides, carbons
• Semiconductor photocatalysts: TiO2, doped Jakšić: Materials, 2010

photocatalysts
(66)

33
 Improved Air Quality -
Photocatalysts
Self-cleaning surfaces: destruction of organic contaminants to
water and carbon dioxide, providing hydrophilic surfaces

Source: Nanoprotect, UK (67)

Compromised Air Quality

• Enclosed spaces after a fire
– Corrosive gases in the air can cause health
and property damage
• Corrosive Drywall homes (CDW)
– Off-gassing sulfur compounds corroding air
conditioner coils and plumbing
• President Obama has pledged to
improve IAQ
– Part of $122 million research initiative to
improve IAQ through HVAC systems, along
with improved energy consumption
(68)

34
 Hazardous Air Pollutants

• NanoScale products have been proven in

the disaster restoration industry to improve
indoor air quality.
• Technology is used to stabilize and mitigate
homes affected by corrosive drywall.
– Product is used in conjunction with
existing HVAC unit
– Destroys corrosive gasses and
hazardous chemical compounds
– Limits further corrosion of metals and
reduces unpleasant and noxious odors

(69)

Disaster Restoration
Sewage Odors (H2S) and Total VOC
14

12
OdorKlenz-Air Cartridge broad range
10
efficacy and enhanced kinetics
8
rapidly reduces TVOC count.
Concentration (ppm)

6 200

4 180

160
2

140
0

0.00 0.50 1.00 1.50 2.00 120

TVOC (ppb)

Time (hr)
100
OdorKlenz Ozone Thermal Fog Carbon Hydroxyl
80

60
TVOC ppb
40

20

0
4:00 PM 6:00 PM 8:00 PM 10:00 PM 12:00 PM 2:00 AM 4:00 AM 6:00 AM 8:00 AM

Time

(70)

35
 Corrosive Drywall
The OdorKlenz process begins working immediately with
dramatic improvement
Perceived Odor Level

Before
Day 5
Day 10

Study CDW Homes (71)

Health Effects and Safety

of NanoActive Materials
• Similar toxicity profile to commercial NanoActive NanoActive
counterparts TiO2* MgO**
– material type, solubility , aggregation Acute Oral
LD50 > 2 g/kg LD50 > 5 g/kg
• Acute and sub-chronic toxicology testing: Toxicity
CHPPM under GLP Acute
– NanoActive materials are no more Dermal LD50 > 5 g/kg -
Toxicity
toxic than their non-nano counterparts
Acute EPA Category
• Human immune cell testing : RMIT- (PII) of “0”
Dermal IV Non-
Non-irritating
University, Melbourne, Australia Irritation irritating
– No cytotoxicity to human immune cells Skin Sensi-
Non-sensitizer Non-sensitizer
tization
• Dermal penetration study: Diagnostic
EPA Category
Medicine/ Pathobiology, Kansas State Acute Eye Practically
III Slightly
University Irritation Non-irritating
irritating
– No penetration of intact human skin Nontoxic Nontoxic
Acute
• Lung effect study Diagnostic Medicine/ 2334 mg/m3 259 mg/m3 for
Inhalation
for 4 h 4h
Pathobiology, Kansas State University
(72)
– No longterm effects

36
Nanotechnology for Other
Environment Related Applications
• Energy harvesting and generation: batteries and
supercapacitors, biofuels, solar cells, fuel cells, hydrogen
production and storage
• Transportation: catalytic converters, fuel additives,
rubber replacements, nanoclay tire sealants, self-
cleaning vehicle coatings
• Protection: self-decon coating (chemical, biological), self-
decon textiles, filtration media (gas masks, antimicrobial
masks)
• Agriculture: pesticide replacement, pesticide destruction
and encapsulation, crop protection (biocidal silver)
• Food: meat processing and packaging (silver biocidal
coatings), barrier plastics (73)

Issues to be Addressed
• Fate and transport of free nanoscale materials in the
environment
• Stability to allow for completed treatment, particle
aggregation
• Persistence in the environment
• Toxicological effects on various biological systems
• Economics of the treatment: site type, type of
contaminants, concentrations of contaminants, extent of
the plume, etc.
• Scale-up: manufacturing costs, sustainability of the
processes
(74)

37
 Thank You

olga@NanoScaleCorp.com
(785) 537-0179
www.NanoScaleCorp.com
(75)

Environmental Applications of Nanotechnology: 
Going Green

Question and Answer Session

38
 Nanotechnology Today 2010
Next Webinar

Benefits and Risk Communication for Nanomaterials
November 16, 2010
11:00 am ‐ 12:30 pm EST

39
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