TiO2 NP Photocatalyzed Degradation of Benzo(a)pyrene Increases Toxicity to Zebrafish
A. Bone1 and R.T. Di Giulio1
Solutions of BaP photocatalytically degraded with TiO2 NP (1ppm) induced more PAH-related toxicity and exposure than solutions of BaP exposed to UV alone, or unilluminated BaP.
NSF EF-0830093
Objective: Determine effect of photocatalytically degrading benzo(a)pyrene using TiO2 NP on larval zebrafish.
Assess toxicity at 48 hpf CYP activity (EROD assay)
Mortality
Control
Expose 5 dpf zebrafish larvae to resultant solutions
Control TiO2 NP BaP
+ TiO2 NP
BaP
Atlas SunTest 2 hours 250 W/m2 1800 kJ/m2
Control TiO2 NP BaP
+ TiO2 NP
BaP
1 Nicholas School of the Environment, Duke University
A
At higher levels of TiO2 NP (>2 ppm), mortality is seen only in these solutions. No mortality occurs in any other treatments (B). Mortality is dose-responsive to both BaP and TiO2 NP concentrations. Increased toxicity is likely due to production of a more toxic BaP daughter product. Chemical analysis of degradation products is underway.
B
C
Environmental Transport & Transformations: Nano Examples from Natural and Engineered Highly Complex (Real) Environments
Nano Iron Oxide Redox Transformations in Minewater Outflow
500 nm
500 nm
500 nm
dissolution, precipitation
Observations Proposed Mechanism
U mine groundwater outflow (anoxic)
Fe2+(aq)
Fe3+(aq) Outflow stream
water (oxic)
Underlying sediment (oxic)
redox boundary
sedimentation, aging
Amorphous silica Iron (oxyhydr)oxides
Green Rust nano-platelets Fe2+
6Fe3+2(OH)18•4(H2O)
Nano Titanium Dioxide (TiO2) in Sewage Sludge and Sewage-Amended Soils
Amorphous iron (oxyhydr)oxides coated with amorphous silica
Particles grow, goethite nanoneedles form from
surface
Agricultural Soils
TiO2 Nanoparticles (NPs) Production & Use
Terrestrial Environment Agricultural Soils
8 weeks incubation in the field after soils amended with Ag NPs-spiked sewage sludge materials.
Sewage Treatment Plant Sewage Sludge Products
TiO2 NPs from sewage sludge products interact with Ag and then enter the environment as a soil amendment.
TiO2 NPs were repeatedly identified across the sewage sludge types tested. They have faceted shapes with the rutile crystal structure, and typically form small, loosely packed aggregates.
200 nm
TiO2
Ag 100 nm
Carol Johnson1, Bojeong Kim1, and Michael F. Hochella, Jr.1
NSF EF-0830093 1Department of Geosciences, Virginia Tech University
Silver Nanoparticles affect Drosophilia Najealicka Armstrong, Malai Ramamoorthy, Delina Lyon, Kimberly Jones, Atanu Duttaroy
Department of Civil and Environmental Engineering, Howard University
NSF EF-0830093
AgNPs interfere with Cu-dependent enzymes, affecting biological processes in the fruit flies.
Armstrong N, et al,(2013) PLoS ONE 8(1): e53186. doi:10.1371/journal.pone.0053186
Attachment Efficiency: Predicting ENM transport and attachment
Delina Lyon1, Shihong Lin2, Stacey Louie3, Ricardo Charles1, Greg Lowry3, Mark Wiesner2, Kimberly Jones1
NSF EF-0830093
Silica
Fe-oxide
Clays
Organic Matter
………
………
………
………
αT= f(αi) α1 α2 α3
• Attachment efficiency, α, can be used to predict NP transport in the environment by using compositional weighted averaged α values.
• Models/theories can be developed to predict α for ENMs and coated ENMs.
1 Department of Civil and Environmental Engineering, Howard University 2 Department of Civil and Environmental Engineering, Duke University 3 Department of Civil and Environmental Engineering, Carnegie Mellon University
Modeling Nanosilver Transformations in Freshwater Sediments
• Due to their tendency to aggregate, nanomaterials are expected to accumulate in the sediments of aquatic systems, where they will undergo chemical transformations that will affect their toxicity as well as their mobility.
• We have developed a 1-dimensional diagenetic model for nano-silver speciation and distribution in freshwater sediments and calibrated it to CEINT mesocosm data.
• This model will be part of an integrated fate and transport model for nanomaterials to be used in environmental risk assessment and will enable the formulation of science-based policy for the regulation of nanomaterials.
Amy L. Dale, Gregory V. Lowry, Elizabeth A. Casman (in preparation) “Modeling Nanosilver Transformations in Freshwater Sediments.”
Amy Dale1, Greg Lowry2, and Elizabeth Casman1 1 Department of Engineering and Public Policy, Carnegie Mellon
University 2 Department of Civil and Environmental Engineering, Carnegie
Mellon University
NSF EF-0830093
Meta-Analysis of in vivo pulmonary toxicity studies
Machine learning techniques produce models relating nanoparticle properties and experimental conditions to indicators of pulmonary toxicity.
Insights gained from these models test hypotheses relating to nano-particle-specific causes of pulmonary toxicity.
Total Dose (ug/kg)
Dia
met
er (
nm)
Change in BAL Neutrophils (fold of control)
0 1000 2000 3000 4000 5000 6000 7000 8000
5
10
15
20
25
30
35
2
2.5
3
3.5
4
4.5
5
Jeremy Gernand and Elizabeth Casman (in review) “A meta-analysis of carbon nanotube pulmonary toxicity studies – how physical dimensions and impurities affect the toxicity of carbon nanotubes. Risk Analysis
Jeremy Gernand and Elizabeth Casman Department of Engineering and Public Policy, Carnegie Mellon University
CN
T
0
0.5 1
1.5 2 x 10 9Heat of Formation (kJ/mol)
Molecular Weight (g/mol)
Group
Period
Atomization energy (kJ/mol)
Mean Isoelectric point
Surface Charge, mV
dHme+ EnFmrGasCat (kcal/mol)
Gibbs Free Energy (kJ/mol)
Density, g/ml
Exposure Mode (1-instillation, 2-inhalation, 3-nasal instillation)
Purity
Animal Species (1-rats, 2-mice)
Gender (1-male, 2-female)
Mean Animal Mass, g
Size or diameter
MMAD, nm
Specific Surface Area, m2/g
Crystallinity
Mass Conc., �g/m3
Exposure Hrs.
Exposure Period, h
Recovery Period, days
Calc Total Dose, mass (ug/kg)
Variable Names
Avg. Variance Reduction Across Forest (Output2)
RF Variable Importance: LDH (fold of control)
positivenegativecategorical
BAL-LDH Response to Metal Oxide* NPs R2 = 0.97
Results facilitate the quantitative comparison of factors contributing to toxicity across studies and elucidate the interactions between such factors.
Interaction of CNT diameter and CNT dose
* TiO2, CeO2, Fe2O3, MgO, NiO, SiO2, ZnO
NSF EF-0830093
Toxicogenomic Effects of Au-NPs on C. elegans O. Tsyusko, J. Unrine, D. Spurgeon, E. Blalock, M. Tseng, D. Starnes, and P. Bertsch
Department of Plant and Soil Sciences, University of Kentucky
NSF EF-0830093 Tsyusko et al. ES&T 2012 46: 4115
• Demonstrated that rme-2 from the endocytosis pathway is involved in Au-NP uptake
• Genes from a C. elegans –specific UPR pathway, such as pqn-5, plays a role in detoxification of Au-NPs
Dis
tanc
e Y
(mm
)
Control Au-NPs Endocytosis and Unfolded Protein Response (UPR)
Trophic Transfer Enhances Bioavailability of Au Nanoparticles J. Unrine, O. Zhurbich, A. Shoults-Wilson, O. Tsyusko and P. Bertsch
Department of Plant and Soil Sciences, University of Kentucky
NSF EF-0830093
0
20
40
60
80
100
120
140
kidney liver muscle
ng Au/g FW
Gavage Au
Worm Au
0
200
400
600
800
1000
1200
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0 500 1000 1500 2000 2500 3000
Bod
y mass (g)
App
aren
t TTF
Days post metamorphosis
Body mass
Apparent TTF
Unrine et al. ES&T 2012 46: 9753
• Demonstrated trophic transfer of Au nanoparticles.
• Showed that trophic transfer enhances bioavailability of nanoparticles.
• Modeled concentrations over lifespan of predator using a biodynamic model.
Fate and Transport of Nano TiO2 at Expected Environmental Concentrations
Ricardo Charles, Delina Lyon, Kimberly Jones Department of Civil and Environmental Engineering, Howard University
NSF EF-0830093
0
0.2
0.4
0.6
0.8
1
1.2
0 5 10 15
Frac
tion
TiO
2 le
ft in
sus
pens
ion
ppm TiO2 in original suspension
0.001 M pH4 C/C0
0.01 M pH 4 C/C0
0.001 M pH 8.3 C/C0 0.01 M pH 8.3 C/C0
0.001 M pH4 no beads 0.01 M pH4 no beads 0.001 M pH 8.3 no beads
Syringe pump
UV Vis
electrolyte
nAg
Batch and column studies allow investigation of TiO2 attachment at low concentrations (~100 ppb).
NISE Net invites CEINT Associate Director to highlight museum-university partnerships CEINT Partnered with NISE Net since 2009- 3 national museum partners Over 17,000 visitors to CEINT partner museums: NanoDays 2009-13 NanoDaysè NanoNightsè Nano Campsè Science Cafesè Educational Video Field trips for museum educators to CEINTèPartner on new Museum grants
Benefits of Museum Partnerships to University Research Center Interested audiences -broad engagement- network facilitates national expansion NISE Net templates help students pitch level for science translation CEINT students value learning science translation Activities demo CEINT research for broad, continuing use
Allows more depth face-to-face public engagement: What roles do microbes play in the environment? How could nanoparticles influence those roles?
NSF EF-0830093
CEINT-NISE Net Partnership- Highlighted as Model
CEINT Video on NISE Net Website Does Every Silver Lining Have a Cloud? Do coatings change where nanoparticles go?
Why are medaka used in CEINT research?
70
75
80
85
90
39.0
39.5
40.0
40.5
41.0
41.5
400 900 1400 1900
COO- stretches NH bend
Gold NPs with Positive or Negative Charge Synthesized to explore the effect of surface charges on transport, transformations,
biouptake and toxicity Stella Marinakos and Jie Liu
Department of Chemistry, Duke University
NSF EF-0830093
Au-‐S O
O-‐ Au-‐S NH3
+
zeta potential: -42 mV zeta potential: +43 mV
Wavenumber (cm-1)
% T
rans
mis
sion
FT-IR
Au@NH3+
Au@COO-
Environmental properties are at least as important as nanomaterial properties in assessing behavior and effects
Ben P. Colman1, Emily Bernhardt1, Jason M. Unrine2, Audrey J. Bone1, Rich Di Giulio1, Paul Bertsch2, Cole W. Matson3, Mark R. Wiesner1, and Gregory V. Lowry4
1Duke University, 2University of Kentucky, 3Baylor University, 4Carnegie Mellon University
NSF EF-0830093
Research must identify macroscopic behavior of nanomaterials in representative environments (e.g. transformations), and the impacts of those behaviors on observed effects.
Resulting sulfidation of AgNPs dramatically decreases toxicity
Organic carbon level in sediment controls Ag NP sulfidation and Ag+ efflux
AND
Mor
e S
ulfid
ized
Darkfield Hyperspectral Imaging Microscopy: Nanoparticle Characterization and Analysis in Complex (Real) Environments
Appala Raju Badireddy1, Jie Liu2 and Mark R. Wiesner1
AgNPs in ultrapure water AgNPs in mesocosm water AgNPs in wastewater water
Type of coating affects the hydrodynamic size of AgNPs
Bundled carboxylated-carbon nanotubes in synthetic water AgNPs in the gut of C. elegans
1 Department of Civil and Environmental Engineering, Duke University 2 Department of Chemistry, Duke University NSF EF-0830093
Modeling the Environmental Release, Transport, Transformation and Biouptake of Nanomaterials: An Integrated Center-wide Initiative
Christine O. Hendren1, Lauren E. Barton1, Paul M. Bertsch2, Elizabeth Casman3, Amy L. Dale3, Gregory V. Lowry3, Mathieu Thérézien1, Jason M. Unrine2, and Mark R. Wiesner1
1Duke University, 2University of Kentucky, 3Carnegie Mellon University
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NSF EF-0830093