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
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Nanotubes
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Transport
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Transformations –
Dissolution
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Agglomeration
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Exposure
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Response
Present day nanoparticles in the environment ●
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Airborne nanoparticles –
Emissions from high temperature sources
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Atmospheric nucleation
Waterborne –
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Colloidal & “dissolved” particles
Mineral –
Asbestos
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Nanocrystals
Biological –
Virus
Exposure assessment ●
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Instruments exist for aerosol nanoparticle measurements –
Size distribution
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Number concentration
Measurements of particles in liquids or on surfaces –
Dynamic light scattering
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Electron or scanning probe microscopy
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Nanoparticles translocate into cells and throughout the body Mechanisms not fully understood Stealth entry of toxic materials into cells –
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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
Present-Day Nanoparticle Exposure ●
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6e4
150 m downwind
dN dlogD
dN dlogD
Combustion –
Diesel engines
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Power plants
High temperature processes – –
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30 m downwind
2e5
Metallurgical Welding
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Grinding
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Ski waxing
Rapid decay with distance from source
0 1
10
100 nm
60 m downwind
1.2e5
0 1 1e4
10
100 nm
300 m downwind
dN dlogD
dN dlogD 0 1
10
100 nm
90 m downwind 1.2e5
0 1 1e4
10
100 nm
300 m upwind
dN dlogD
dN dlogD 0 1
10
100 nm
0 1
Zhu, Hinds, Kim and Sioutas J. Air & Waste Manage. Assoc. 52:1032-1042
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100 nm
Wind Direction
Nanoparticle Exposures are Transient
Exposures on Los Angeles freeways
DMA size distribution measurements
Ambient and filtered, incabin data
Low nanometer particles difficult to measure
Homogeneous Nucleation in the Atmosphere
Boy and Kulmala, Atmos. Chem. Phys. 2: 1-16 (2002)
Nanoparticles ●
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Adverse health effects –
Cardiovascular effects
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Translocate across cell membranes
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Bypass blood-brain barrier
Produced by homogeneous nucleation from the vapor phase –
Combustion systems, high temperature processes
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Photochemical smog
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Nanotechnology
Limited data on environmental/health implications of nanotechnology –
Toxicity
DMA
DMA
CPC
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 + + + + + + + + + + + + + + + + + + -
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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 ●
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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
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We don't know the risks of engineered nanomaterials Risks may depend on –
Composition
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Size
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Morphology
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State of aggregation
Data are needed to assess risks
Conclusions ●
Most risks of nanotechnology should be manageable but
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The cost of not identifying potential risks may be high Will nanotechnology become the next genetically modified crop?
Conclusions ●
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Real-time measurements of airborne nanoparticles are now possible –
Size distribution
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Chemical composition as a function of particle size
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Expensive and complex
New instruments should soon become Measurements of nanoparticles in water or on surfaces are not well developed –
Dynamic light scattering
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Electron microscopy
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Electrophoretic separations ●
Need detection technology
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Charge???
Acknowledgments ●
Nick Brunelli
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Donald Collins (Texas A&M University)
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Andrew Downard
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Harmony Gates
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Lynn Russell (Scripps)
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Jian Wang (Brookhaven)
Support ●
Office of Naval Research
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Davidow Foundation
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Coordinating Research Council
Capillary Electrophoresis Electrode
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Capillary Surface
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Power Supply