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