Nanoparticles in the Environment

Transcription

1 Nanoparticles in the Environment W. Ball: Very (!) brief introduction to Engineered Nanoparticles (ENPs) W. Ball presentation of M. Wiesner* slides on Nanoparticle Behavior in Complex Environments * Center for the Environmental Implications of NanoTechnology (CEINT)

2 Environmental Transport, Transformation, and Fate

3 Consumer Goods and Technologies Containing Nanomaterials

4 Thousands of manufacturer identified nanotechnology based consumer products currently on the market Woodrow Wilson International Center for Scholars

5 Inorganic ENPs Engineered Nanoparticles Carbon Nanotubes Single Walled Carbon Materials Properties Nanotube (SWCNT) Mechanical Strength Electrical Conductivity High Aspect Ratio Multi Walled Carbon Nanotubes (MWCNT)

6 Rational development of safe by design nanomaterials will require knowledge of how intrinsic nanoparticles properties (size, shape, surface chemistry) impact environmentally relevant properties (colloidal stability, sorption properties) E.g. Impact of Surface Chemistry on sorption properties of carbon nanotubes Naphthalene Zn 2+ (aq) Oxidized Carbon Nanotube Sorption capacity Sorption Capacity Atomic Percentage of Surface Oxides Surface Oxygen Concentration (Atomic %) Cho et al., Env. Sci. Technol. 43: 2899 (2008) Cho et al., Langmuir, 26:967 (2010)

7 Probing the Influence of Surface Chemistry on Engineered Nanoparticle Behavior, Fate and Effects in Aquatic Environments e.g., surface modification of MWCNTs Surfactant Adsorption Surface Oxidation Natural Organic Molecules OH after Smith et al. Environ. Sci. 43: 819(2009).

8 Stream Dynamics and Chemical Transformations Control the Environmental Fate of Silver and Zinc Oxide Nanoparticles in a Watershed-Scale Model Amy L. Dale, Gregory V. Lowry, and Elizabeth A. Casman * Engineering and Public Policy, Carnegie Mellon University Civil and Environmental Engineering, Carnegie Mellon University Environ. Sci. Technol., Article ASAP (2015) DOI: /acs.est.5b01205

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10 A little more bio information..

11 Some take home points: (WPB addition, based on summary comments from MRW) Nanoparticles (whether engineered [ ENPs ] or natural): can be taken up by plants and animals; NPs are subject to trophic transfer in some cases with biomagnification, in some with dilution; Attachment efficiencies appear to be a promising way of predicting NP behavior. The toxicity issue is secondary. Most important growing awareness of: Complexity of nanometric phases in their interactions with living systems; and Potentially important roles of NPs in uptake of chemicals, nutrient cycling, transport of other species, etc.

12 Nanomaterial behavior in complex environments Mark R. Wiesner Director Center for the Environmental Implications of NanoTechnology Duke University

13 Composition Bandgap Size Nanoparticle Properties Production amounts Ambient Concentrations Effective dose Exposure Hazard Mortality Development Population Nutrient cycling RISK

14 Product life cycles and value chains Product use behaviors ENM production magnitudes Social Properties Composition Bandgap Size Nanoparticle Properties Surface affinity Surface charge/ potential (ζ-potential) Aggregation rate Hydrophobicity System Properties ph, NOM, Ionic strength, Surfaces (biotic, mineral, organic ) Fluid flow, temperature Exposure Hazard RISK

15 Social Properties Nanoparticle Properties System Properties Functional Assays Measurement in prescribed system Quantifies a meaningful process for exposure, hazard or both Exposure Hazard RISK

16 Functional Assay Focus Fate & Transport Example Social & Engineered Properties Mass Available Release Rate i = speciation Material Properties (Intrinsic) Core Size Band Gap Composition System Derived Material Phenomena Steric Effects Hydrophobicity DLVO NOM System Properties Proteins Ionic Strength ph!!!!!" = ±!"!!!!!!"#!"#$%&"'!! +!!"#$%&'"(!! +!!"#$%!"#$%&'"(!! +!!"#$%&'()!! +!!"#$%&!"#$!!! Adsorption Settling Aggregation Deposition Precipitation Sulfidation Bioproduction Complexation Photosensitization Concentration Speciation EXPOSURE HAZARD Mutagenicity Carcinogenicity Mortality RISK

17 Translocation of Au NPs in Nicotiana xanthi 30 nm Au-citrate NPs Judy et al., ES&T 46:

18 Effect of Particle Size and Shape on Reactivity Figure 1. A) SEM and B) AFM images of unsulfidized AgNP arrays produced by NSL. C) AFM image of an AgNP array after a 2-d exposure to 10 µm Na 2 S. D) AgNP height distributions before (black) and after (red) the exposure. Median Height (nm) ph Time (h) Figure 3. AgNP dissolution in 1 mg/l NaOCl at ph 6.5. Error bars are standard deviations of triplicate samples. Kent and Vikesland, Environ. Sci. Technol., 2012, 46 (13), pp

19 Sulfidation of Ag, ZnO, and CuO NPs Ag +HS - Ag 2 S ZnO +HS - ZnS CuO +HS - Cu x S y Ma et al., 2013 ES&T 47 (6), pp ; Levard et al., ES&T (12), Ma et al., 2014 ES Nano

20 Mode of Uptake of Ag by Duckweed Duckweed Landoltia punctata 18 h AgNO 3 AgNPs Ag 2 S-NPs ~60 h Dead Stegemeier et al., ES&T (in preparation)

21 Sulfidation Decreases Toxicity Zebrafish Killifish C. Elegans Duckweed Levard, Hotze, et al., ES&T 2013, 47,

22 Real World Transformations Wastewater Treatment Plant Freshwater Wetland

23 ZnO Fate in the Wastewater System? Primary clarifier (180 L) Anaerobic digester (150 L) \Secondary clarifier (150 L) Zn 2+ Control ZnO NP

24 Mesocosms: Controlled Release Field Sites! 30 mesocosms! year-long experiments! pulse & chronic inputs! Nano- Ag, CeO2, Cu, Au, TiO2, SWCNTs! NPs+conventional contaminants! Release form commercial productions

25 Mesocosm Results 100% Mesocosm Toxicity - 24 h post dosing Fundulus Larval Mortality Mortality (+/- SEM) 80% 60% 40% 20% Laboratory Spiked - 48 h Mesocosm - 48 h 0% NSF EF

26 Bioaccumulation & Trophic Transfer of NPs 1 Joel Meyer 2 Paul Bertsch and Jason Unrine 3 Bernhardt, Richardson & Gunsch 4 Hunt YES 2 YES YES 2 YES 1,2 YES 1,2,3 YES 2,3 YES 1,2,3

27 Au IV Au foil Hot spot Au Lα XANES Judy et al., 2011 ES&T

28 <1 mg kg-1 Trophic transfer & dilution of Au NPs Rana catesbeiana ~10 mg kg-1 Eisenia fetida ~100 mg kg-1 Unrine et al. ES&T 2012

29 What parameters are needed to predict transport and fate of nanoparticles/

30 Affinity of nanoparticles for various surfaces deposition & heteroäggregation homoäggregation

31 Aggregation, Transport and Surface affinity dn k dt = 1 2 α β ( i, j )n i n j αn k β i,k i+ j k Aggregation: Dissolution Reactivity Photo-catalysis Molecular Adsorption transport Deposition: Environmental dispersal Biouptake Translocation in organisms i ( ) n i +/- breakup settling dissolution Hotze et al., Langmuir 2010, 26(13), Jassby et al., Environ. Sci. Technol. 2012, 46,

32 Nanosilver concentration in water column of mesocosm following pulse input

33 Simulations of heteroaggregation!

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35 Measuring surface affinity (alpha) in model systems detector Breakthrough curves GB data acquisition porous medium Tracer C/Co syringe pump flow measurement gear pump feed solution Pore Volumes

36 Measuring surface affinity in complex systems dn k dt = 1 2 α β ( i, j )n i n j αn k β i, k i+ j k i ( ) n i breakup ln( γb +1) = αβ ( n, B)Bt Barton et al., ENVIRONMENTAL ENGINEERING SCIENCE Volume 31, Number 7, 2014

37 Transformed distribution coefficient aggregation time ln γb +1 ( ) = αβ n, B ( )Bt Barton et al., ENVIRONMENTAL ENGINEERING SCIENCE Volume 31, Number 7, 2014

38 Conceptual model for nanoparticle reactivity transport attachment reaction / effect β α k

39 Importance of surface affinity for transformtion: CeO2 CeO2 CeO2-citrate stabilized Barton et al (in review)

40 Ag NP Embryotoxicity across a Salinity Gradient The Role of CoaJngs and Dissolved Silver 100% 80% Toxicity Atlan?c killifish Fundulus heteroclitus Mortality (+/- SE) 60% 40% 20% 0% GA PVP Salinity Ag NP coa?ngs significantly affect par?cle behavior Stability/Aggrega?on (Ag- gum arabic most stable) Toxicity (Ag- gum arabic most toxic) Dissolved silver and silver specia?on play a significant role in toxicity Toxicity curve shape related to silver specia?on (total dissolved Ag, not Ag + ) CIT CHESS Model Dissolved Ag AgNO3 4 µm Ag- PVP 50 mg/l Ag- citrate 50 mg/l Ag- GA 5 mg/l Hydrodynamic Diameter (nm) Colloidal Stability PVP CIT GA Salinity ( ) Ag- PVP 100 mg/l Ag- citrate 50 mg/l Ag- GA 5 mg/l Auffan et al., Nanotoxicology, 2013, Bone et al, ES&T 2012

41 Examples of nanoparticle reactivity Effect Toxicity to plants and fish by nano Ag Viral inactivation by fullerol Bacterial inactivation by CeO2 Underlying reaction Nano silver dissolution Singlet oxygen generation Ce reduction heteroäggregation n B n-b 1 = 1 1 +!!!!"#!!"!"#! reaction n* P B*!! =!!"#!!"!"#!!"# +!!"!"#!

42 Importance of surface affinity for transformtion: CeO2 Alpha = 0.16 Alpha = 0.07 Barton et al (in review)

43 Particle deposition and translocation in organisms

44 Summary 1. Need for functional assays (like surface affinity) for key processes (Transport, transformation, bioüptake ) 2. Many interactions between nano-scale materials, organisms and ecosystems- RICH SCIENTIFIC TERRAIN

45 Some take home points: (WPB addition, based on summary comments from MRW) Nanoparticles (whether engineered [ ENPs ] or natural): can be taken up by plants and animals; NPs are subject to trophic transfer in some cases with biomagnification, in some with dilution; Attachment efficiencies appear to be a promising way of predicting NP behavior. The toxicity issue is secondary. Most important growing awareness of: Complexity of nanometric phases in their interactions with living systems; and Potentially important roles of NPs in uptake of chemicals, nutrient cycling, transport of other species, etc.

46 Greg Mélanie Jason Lowry Auffan Unrine Jean-Yves Christine Bottero Hendren Thank You Paul Bertsch Mike Hochella Rich Di Giulio Cole Matson Emily Bernhardt Liz Casman Joel Meyer Peter Vikesland Clement Levard Gordon Brown Paul Westerhoff Olga Tsyusko Raju Badireddy Shihong Lin Yao Xiao Fabienne Schwab Lauren Barton Mathieu Terezien Jeff Farner David Jassby Benjamin Espinasse Charles De Lannoy Alexis Carpenter Amalia Turner