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Nanoparticles in the Environment:

The Measurement Challenge

Richard C. Flagan
Chemical Engineering
and
Environmental Science and Engineering
California Institute of Technology
Pasadena, CA
USA
Is Nanotechnology a Hazard to the Environment?
● Entry into the environment
– Nanoparticles
– Nanotubes
– ......
● Transport
● Transformations
– Dissolution
– Agglomeration
● Exposure
● Response
Present day nanoparticles in the
environment
● Airborne nanoparticles
– Emissions from high temperature sources
– Atmospheric nucleation
● Waterborne
– Colloidal & “dissolved” particles
● Mineral
– Asbestos
– Nanocrystals
● Biological
– Virus
Exposure assessment
● Instruments exist for aerosol nanoparticle
measurements
– Size distribution
– Number concentration
● Measurements of particles in liquids or on
surfaces
– Dynamic light scattering
– Electron or scanning probe microscopy
● Nanoparticles translocate
into cells and throughout
the body
● Mechanisms not fully
understood
● Stealth entry of toxic
materials into cells
– Nanoparticles
dissolve after entry
into cell
● Nanoparticle therapeutics
<10nm eliminated
through kidneys
– Entry into wastewater
Moore, Environment International 32 (2006) 967–976
Cytotoxicity (murine macrophage cell viability) versus concentration

K.F. Soto, A. Carrasco, T.G. Powell, K.M. Garza and L.E. Murr. J. Nanoparticle Res. (2005) 7: 145–169
What evidence is there for direct
effects of inhaled nanoparticles on
human health?
What evidence is there for direct
effects of inhaled nanoparticles on
human health?

Ambient air pollution exposures


30 m downwind 6e4 150 m downwind
Present-Day 2e5

Nanoparticle
dN
Exposure dN
dlogD dlogD

● Combustion
0 1 0
– Diesel engines 10 100 nm 1 10 100 nm
60 m downwind 1e4 300 m downwind
– Power plants 1.2e5

● High temperature
dN
processes dN
dlogD
dlogD

– Metallurgical
0
0
– Welding 1 10 100 nm 1 10 100 nm
90 m downwind 300 m upwind
– Grinding 1.2e5
1e4

– Ski waxing
dN
dN
● Rapid decay with dlogD
dlogD

distance from
source 0
0
1 10 100 nm 1 10 100 nm
Zhu, Hinds, Kim and Sioutas J. Air & Waste Manage. Assoc. 52:1032-1042
Wind Direction
Nanoparticle
Exposures are
Transient

 Exposures on Los
Angeles freeways

 DMA size distribution


measurements

 Ambient and filtered, in-


cabin data

 Low nanometer particles


difficult to measure
Homogeneous Nucleation in the Atmosphere

Boy and Kulmala, Atmos. Chem. Phys. 2: 1-16 (2002)


Nanoparticles
● Adverse health effects
– Cardiovascular effects
– Translocate across cell membranes
– Bypass blood-brain barrier
● Produced by homogeneous nucleation from the
vapor phase
– Combustion systems, high temperature processes
– Photochemical smog
– Nanotechnology
● Limited data on environmental/health
implications of nanotechnology
– Toxicity
CPC
DMA
DMA

RDMA
Opposed Migration Aerosol Classifier

Flagan, RC. 2004. Opposed Migration Aerosol Classifier (OMAC). Aerosol Sci. Technol. 38 (9): 890-899.
Can we extend these
measurements to particles in water?
Radial-Symmetric FFE
Double Layer

+ + + + + + + + + + + + + + + + + +

- - - -
-

+ + -
+
- -
+
-
- - - + -
+
+ -
+
-
+ + -
+ +

+ + + + +
- - - - - - - - - - - - - - - - - - - - - - V
Differential mobility analyzer
will not work in water,
but there are other approaches that do.
Free Flow
Electrophoresis

Peterson and Cliffel (2005)


Analytical Chemistry. 77: 4378.
Electrophoretic Separations of Nanoparticles
in Water are Possible,

but
● Charge depends on particle and solution
chemistry
● Single particle detection is not available
● Optical detection of ensemble is strongly
size dependent
● New methods are needed to enable
nanoparticle measurements in the
aqueous environment
Conclusions
● Nanoparticles can cause health problems
but
● We don't know the risks of engineered
nanomaterials
● Risks may depend on
– Composition
– Size
– Morphology
– State of aggregation
● Data are needed to assess risks
Conclusions
● Most risks of nanotechnology should be
manageable
but
● The cost of not identifying potential risks may
be high
● Will nanotechnology become the next
genetically modified crop?
Conclusions
● Real-time measurements of airborne nanoparticles are now
possible
– Size distribution
– Chemical composition as a function of particle size
– Expensive and complex
● New instruments should soon become
● Measurements of nanoparticles in water or on surfaces are not
well developed
– Dynamic light scattering
– Electron microscopy
– Electrophoretic separations
● Need detection technology
● Charge???
Acknowledgments
● Nick Brunelli
● Donald Collins (Texas A&M University)
● Andrew Downard
● Harmony Gates
● Lynn Russell (Scripps)
● Jian Wang (Brookhaven)
Support
● Office of Naval Research
● Davidow Foundation
● Coordinating Research Council
Capillary Electrophoresis

Electrode
Capillary Electrode
Surface

- - - - - - - - - - - - - -
+ + + + + + ++
- - - - -
+ - + - + + - -
+ - - + + -
- +
+ + + + + + + +
- - - - - - - - - - - - - -

Power Supply