Nanotechnology and the Environment OSWER Conference July 12-13, - - PDF document
Nanotechnology and the Environment OSWER Conference July 12-13, Washington DC Dr. Vicki Colvin Director, CBEN Professor of Chemistry Rice University Small is Beautiful Huge surface Highly areas crystalline C-sixty Cadmium Selenide
Director, CBEN Professor of Chemistry Rice University
C-sixty 1nm Cadmium Selenide nanocrystal 6 nm Lysozyme 3 nm
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Introduction: Overview of Nanotechnology and the Environment
20 NANOTECHNOLOGY AND OSWER New opportunities and challenges July 12-13, 2006 Washington DC
BiMetallic Catalysts
Removing TCE in water
Nanogold on silica
Tumor capillary Carcinoma cells
Shrinking Tumors
50 nm
Magnetite particles
Water purification
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200 400 600 800 1000 1200 1400 2002 2003 2004 2005 2006 2007 Year Nanotechnology R&D - US Govt in Millions $$$
10,000 20,000 30,000 40,000 50,000 60,000 70,000 80,000 90,000 1999 2000 2001 2002 2003 2004 2005 Year # Nanotechnology Publications
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Nano- technology
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Small size provides high surface area In-situ remediation of contaminated wells Small size provides reactive surface 100-fold improvement in TCE removal
receptor waste pit dissolved groundwater plume
500 1000 1500 2000 2500 20 40 60 80 100 wt % Pd Rate
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Ayotte et al, Envi. Sci. Tech. 2003 37, p.2075
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“ Our two year study showed that none of the (18) Arsenic Removal Plants could maintain arsenic in … water … below the WHO guidelines ….”
Waste to Sorbent 1 gram treats Backwash Material dispose of kg (1 (kg) / month ____ L water frequency (day) yr)
Alumina + Metal Oxide
Red Mud [As(III)]
For a family of four, using 900 L water/month, at 500 ppb As levels (7.9 pH)
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* D. M. Sherman, S. R. Randall Geochimica et Cosmochimica v. 67 no. 22 p. 4223
MASON TOMSON, AMY KAN, SUJIN YEAN
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http://www.kemcointernational.com/IronOxide.htm
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500 1000 50 100
C (ug/L) q (mg/Kg)
500 1000 50 100 C (ug/L) q(mg/Kg) As(III), pH 6.2 As(V), pH 6.2
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NP Surface Area in 1 gram
50 100 150 200 250 300 5 10 15 20 Radius (nm) Surface area (m2/gm) Iron Oxide NP
Commercial Magnetite
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From Kemico, avg size 20 nm 26.88 ± 2.26 nm 13.96 ± 1.62 nm 9.11 ± 0.88 nm
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Particle Size (nm) Volume
(L) 12 As(III) 2,283 20 As(III) 594 300 As(III) 21 12 As(V) 1,435 20 As(V) 1,145 300 As(V) 150
As (III)
25,000 50,000 75,000 100,000 125,000 150,000 175,000 200,000 5 10 15 20 25 C (mg/L) q (mg/kg)
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Small cluster: Supraparamagnetic Easy to magnetize
Larger cluster: Single Domain Bulk solid: Permanent magnet Magnetization can shift Small magnetization
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29 NANOTECHNOLOGY AND OSWER New opportunities and challenges July 12-13, 2006 Washington DC
No field With field
No field, recovery
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Kakihara, Y., T. Fukunishi, et al. (2004). "Superconducting high gradient magnetic separation for purification of wastewater from paper factory." Ieee Transactions on Applied Superconductivity 14(2): 1565-1567.
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A B
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Number of Particles Number of Particles100 nm
1000 600 100 350 500 300 80 800 80 Number of Particles Number of Particles 250 Number of Particles Number of Particles 400 Number of Particles Number of Particles 60 40 Y Axis Title 60 40 600 400 200 150 100 300 200 20 200 100 50 20 20 25 30 35 40 45 8 10 12 14 16 18 8 10 12 14 16 18 20 22 24 26 Size (nm) 6 8 10 12 14 16 18 20 22 24 5 10 Size (nm) 15 20 25 Size (nm) X Axis Title Size (nm)26.88 ± 2.26 nm 19.56 ± 2.14 nm 13.96 ± 1.62 nm 12.40 ± 1.54 nm 12.18 ± 1.10 nm
1200 700 800 1000 140 1000 600 700 120 800 600 500 400 300 600 400 Number of Particles 800 600 400 500 400 300 200 100 80 60 40 200 200 200 100 100 20 8 10 12 14 16 18 20 22 24 26 5 10 15 20 25 2 4 6 8 10 2 4 6 8 10 12 Size (nm) 6 7 8 9 10 11 12 Size (nm) Size (nm) Size (nm) Size (nm)11.72 ± 1.03 nm 10.90 ± 1.90 nm 9.11 ± 0.88 nm 4.35 ± 0.68 nm 3.95 ± 0.63 nm
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100 90 80 70
19.56 nm 12.40 nm 6.00 nm 3.95 nm % Retention 9.11 nm
50 40 30 20 10 60 0.0 0.1 0.2 0.3 0.4 0.5
Magnetic Field (T)
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~ 3 Periodic 14
Backwash Frequency (day)
~7.5 to 75 [2] 0.014 ~0.003 0.003
Efficiency[1]
1.1 4328.13 2.883
Annual waste to dispose kg [3]
10 0.09 Nanoscale Iron Oxides No Removal of Toxic As(III) Ion Exchange 0.002 360.7 Red Mud [As(III)] 3.8 0.24 Alumina + Metal Oxide
1 gram treats ____ L water Sorbent (kg)/ month Material
1. “Efficiency” as defined by NAE in the "Granger Challenge, June, 2005" The object is to maximize the efficiency. 2. 12 nm magnetite cost estimated as a synthesized chemical at $2.00/lb and a multiplication factor of cost by 3x to 30x for estimated conditioning chemicals and packaging. 3. The amount (kg) + the backwash frequency
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Introduction: Overview of Nanotechnology and the Environment
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Effective water treatment systems using nanoparticles Grand Challenges 2011 Outcomes A nano-enabled water treatment system applied on a large scale
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Cadmium Selenide nanocrystal 6 nm C-sixty 1nm Lysozyme 3 nm
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End-of-use issues: Ecological impacts Worker and laboratory safety Direct consumer contact
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From Powder From Toluene
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Syringe Pump Auto- Sampler Soil Column nC60
Flow Velocity: v = 5 ft/d
500 nm
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(MIC in ppm)
Lyon, D. Y., L..K. Adams, J.C. Falkner, P.J.J. Alvarez. Environ. Sci. Technol.; (Article); 2006; Adams, L.K., D.Y. Lyon, P.J.J. Alvarez. Comparative EcoToxicity
More toxic Less toxic 10-1 100 101 102 103 104 Nano-SiO2 Nano-TiO2 Nano-ZnO “Nano” does not mean toxic for many materials C60 w/PVP C60/THF C60/toluene C60 effects depend on how it is water solubilized
200 nm
Nano-TiO2 Nano-C60
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Zebrafish larva with pericardial edema due to nC60 exposure
20 40 60 80 100 48 60 72 84 96 108 120 Hours Post-Fertilization Pericardial Edema (%) nC60/THF nC60/THF+GSH
Mitigation by GSH suggest that toxicity is related to oxidative stress
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Live Dead
1) Nolan J S; Packer L Monolayer culture techniques for normal human diploid fibroblasts. METHODS IN ENZYMOLOGY (1974), 32(Part B), 561-8. 3) LIVE/DEAD Viability/Cytotoxicity Kit (L-3224). Molecular Probes Operation Manuel. p. 1. 1999.
C60 colloidal Particles (4 ppm)
DMEM HDP cells, seeded
(Human Diploid Fibroblasts)
48 Hours
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10
0 10 1 10 2 10 3 10 4 10 5 10 6
20 40 60 80 100 120
% Dead
HDF HepG2 NHA
0.002 NHA 0.02 HDF 0.05 HepG2 LC50 (ppm) Human Cell Line
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11,000 THF 1,600 Toluene 10 Benzo[a]pyrene* 0.02 n-C60 100 Paraquat 0.001 Dioxin* 17,000 Ethyl Alcohol* > 100,000 C60-(OH)x LC50, mg/kg Toxin
* National Institute of Health, Registry of Cytotoxicity Data (ZEBET)
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Control Control HepG2 HepG2 and C and C60
60
No dye 10,000 70,000 500,000
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t = 70 min t = 110 min
1 um
t = 20 min t = 70 min t = 110 min
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O HOH O
2
OO OO
radical
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OH OH OH OH HO HO OH OH HO HO HO OH OH HO OH OH O O O O O O O O Na Na Na Na Na Na Na Na
10
10
10 10
2
10
4
10
6
10
8
20 40 60 80 100
% Dead Fullerene Species Concentraion (ppb)
COOH HOOC HOO C HOOC HOOC COOH
In Increasing derivatization lowers photoinduced singlet oxygen generation More polar functionality creates higher water solubility in materials
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OH OH OH OH HO HO OH OH HO HO HO OH OH HO OH OH O O O O O O O O Na Na Na Na Na Na Na Na
10
10
10 10
2
10
4
10
6
10
8
20 40 60 80 100
% Dead Fullerene Species Concentraion (ppb)
COOH HOOC HOO C HOOC HOOC COOH
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10
10
1
10
2
10
3
20 40 60 80 100
% Dead SWNT Concentration
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22 nm Fe3O4 in hexanes
Solution before After column (one pass) After recovery/wash
10 nm Fe3O4 in water 30 nm Fe3O4 commercial
No recovery 1 Tesla Magnetic fields .1 Tesla Magnetic fields
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Particle Size (nm) As(V)
As(III) Initial As Concentration (mg/L) Residual As Concentration (mg/L) % Removal 12 As (III) 500 3.9 99.2 20 As (III) 500 45.3 90.9 300 As (III) 500 375.7 24.9 12 As (V) 500 7.8 98.4 20 As (V) 500 17.3 96.5 300 As (V) 500 354.1 29.2
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