Environmental Implications of Nanotechnology. Christine Ogilvie Hendren, PhD
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1 Environmental Implications of Nanotechnology Christine Ogilvie Hendren, PhD CEINT Executive Director Association of Public Health Laboratories Annual Conference Nanotechnology: The Sleeping Giant of Public Health?
2 Breaking the Cycle of Unintended Consequences Mercury amalgamation for precious metals mining Pesticides for control of disease Chloroflurocarbons (CFCs)
3 Outline Context: What is new or unique about nano? New ability to observe and control matter at the nanoscale Extreme broad scope requires interdisciplinary collaboration Approach: How to assess the environmental risks of nanomaterials? Integrate broad expertise in pursuit of targeted research questions Measure the right things to answer those questions Iterative feedback between disciplines, experimental scales, and models Continuous focus on enabling decisions Environmental forethought: We have the opportunity to get nano right!
4 Nanotechnology Nanotechnology is the understanding and control of matter at dimensions between approximately 1 and 100 nanometers, where unique phenomena enable novel applications *. Encompasses nanoscale science, engineering, and technology, and involves imaging, measuring, modeling, and manipulating matter at this length scale. * National Nanotechnology Initiative,
5 Nano Scale Meters nm 450 nm Dissolved organic matter Dissolved metal complexes Polynuclear cluster Nanoparticles Hemoglobin Smoke from fire Volcanic ash Sea spray Automobile exhaust Colloids Viruses Bacteria 10 kda filter 0.45 m filter Dissolved Colloidal Particulate
6 Unique Properties at the Nanoscale Materials manufactured to ~1-100 nm in size exhibit unique properties due to their small size (relative to larger materials). Auffan et al., Nature Nano, 2009
7 Unique Properties at the Nanoscale Materials manufactured to ~1-100 nm in size exhibit unique properties due to their small size (relative to larger materials).
8 Engineered Nanomaterials Timeline 1857 Michael Faraday discovered colloidal ruby gold, demonstrating that nanostructured gold under certain lighting conditions produces different-colored solutions Rice University researchers Kroto, O Brien, Curl, and Smalley discovered the Buckminsterfullerene (C60), or buckyball, a previously unknown form of pure carbon. The team was awarded the 1996 Nobel Prize in Chemistry Early 2000s Consumer products making use of nanotechnology began appearing in the marketplace. FUTURE Electronics Sustainable energy Clean water Targeted drug delivery 1947 The semiconductor transistor is discovered at Bell Labs, laying the foundation for electronic devices and the Information Age Don Eigler and colleagues spelled the IBM logo in atoms by literally moving 35 xenon atoms on a background of copper atoms to spell out the letters ~ 2003 NNI: National Nanotechnology Initiative NEHI: Nanotechnology Environmental and Health Implications Disease detection Sensors Sustainable transportation Everyday materials
9 Responsible Nanotechnology THE NOVEL PROPERTIES OF ENGINEERED NANOMATERIALS THAT INSPIRE NEW PRODUCTS WILL OFTEN BE THE SAME PROPERTIES THAT POSE RISKS
10 Applications & Implications Peptide coatings can help nanoparticles slip into cells, a process that may prove useful for in vivo imaging or drug delivery if scientists can clear up how it works. Clathrin-Mediated Endocytosis of Quantum Dot Peptide Conjugates in Living Cells, Anas et al., ACS Nano, 2009, 3 (8), pp via C&EN News
11 Impacts Electronics Energy and Environmental Applications
12 Impacts TiO 2 in China TiO 2 in Korea
13 Impacts Dumping Grounds in Accra, Ghana
14 Research to inform Risk-Based Decisions HAZARD x EXPOSURE = RISK Hazard, No Exposure No Hazard, Exposure No Risk No Risk Hazard AND Exposure RISK
15 If nanomaterials pose risk, what are the options for managing it? HAZARD x EXPOSURE = RISK Material substitution Material modification Out-right ban Handling practices Treatment/ remediation Green-chemistry Reduce bioavailability Reduce/ engineer mobility Persistence
16 Comprehensive Environmental Assessment Framework How much of a material is there? OH - OH - OH - OH - How much gets into the environment? Where does it go? How does it change? Is it bioavailable? How much gets into plants, animals, ecosystems? How much does it take to make something bad happen?
17 Mandatory Interdisciplinary Approach ENM Detection & Measurement Market Analysis ENM Characterization Life Cycle Assessment Bio-Geo- Chemistry Fate and Transport Economics Exposure Dosiemetry Human & Eco Toxicology
18 Center for the Environmental Implications of NanoTechnology (CEINT) Headquartered at Duke University, 7 US Universities Funded by NSF and EPA in 2008, renewed in 2013 CEINT s Vision: Elucidate principles that determine nanomaterial behavior in the environment Translate this knowledge into language of risk assessment Provide guidance to assess existing & future concerns surrounding environmental implications of nanomaterials Educate next generation of scientists and engineers
19
20 Outline Nearly infinite possible materials and interactions Persistent uncertainty In light of Concurrent research and need for near term decisions The CEINT approach is: Integrate broad expertise in pursuit of targeted research questions Measure the right things to answer those questions Iterative feedback between disciplines, experimental scales, and models Continuous focus on enabling decisions
21 CEINT Research Focus CEINT organizes a comprehensive effort looking at the environmental implications of nanotechnology with a focus on: Exposure, transport and transformation Effects in complex, real-world systems Risk Forecasting to inform decision-making
22 The old way of nano risk thinking What is it? Nanomaterial System Descriptors Properties What can happen because of it? Nanoparticle Impacts
23 How do we answer: What is it? Describe a man Male Hungry 5 10 Laughing Blue Grey eyes Standing Intrinsic Properties Fundamental to identity Do not change Extrinsic Properties Still describe the person in question Change as a function of system properties
24 How do we answer: What is it? Static Male Changing Male 5 10 Blue eyes State 1 Hungry Frowning Seated 5 10 Hungry Laughing Male 5 10 Blue eyes State 2 Full Laughing Standing Blue eyes Standing Male 5 10 Blue eyes State 3 Starving Yelling Jumping
25 How do we answer: What is it? System 1 Male On an airplane on a 6 hour flight 5 10 that doesn t serve snacks. Blue eyes All systems are NOT created State 1 equal Hungry Quite Frowning possibly Seated important System 2 Male At tonight s poster reception and 5 10 cocktail hour. Blue eyes State 2 Full Definitely Laughing important Standing Apocalypse. System 3 Male 5 10 Blue eyes State 3 Starving Not a good Yelling use of Jumping resources
26 How do we answer: What is it? Core composition Band gap Particulate diameter State 1 Surface composition 1 Surface charge 1 Aggregation state 1 System 1 In a WWTP secondary clarifier Core composition Band gap Particulate diameter State 2 Surface composition 2 Surface charge 2 Aggregation state 2 In surface water System 2 Core composition Band gap Particulate diameter State 3 Surface composition 3 Surface charge 3 Aggregation state 3 In stomach acid System 3
27 Separating Nanomaterial and System Properties Material & System Properties Material Impacts What is it? What can happen because of it? Nanomaterial System Descriptors Properties Intermediate Descriptors of Interactions between Material and System Properties Nanoparticle Impacts still doesn t get us there.
28 Snapshots of Nanomaterial and System Properties Time-of-flight mass spectra of carbon clusters prepared by laser vaporization of graphite and cooled in a supersonic beam. Scanning electron micrograph (SEM) of SWNT material. H. W. Kroto, J. R. Heath, S.C. O'Brien, R. F. Curl, and R. E. Smalley (1985) C60: Buckminsterfullerene, Nature, 318. A. Thess et al. (1996) Crystalline Ropes of Metallic Carbon Nanotubes, Science, 273.
29 Snapshots of Nanomaterial and System Properties
30 Snapshots Outcomes Various materials in various systems and states Hazardous outcome
31 Snapshots Measurable Functional Indicators Outcomes Various materials in various systems and states Need: Functional Intermediate Indicators Have to be measurable Have to tell us something about what is happening in the system Hazardous outcome
32 Snapshots Measurable Functional Indicators Outcomes Various materials in various systems and states Need: Functional Intermediate Indicators Have to be measurable Have to tell us something about what is happening in the system Hazardous outcome
33 Snapshots Measurable Functional Indicators Outcomes Various materials in various systems and states Need: Functional Intermediate Indicators Have to be measurable Have to tell us something about what is happening in the system Hazardous outcome
34 Snapshots Measurable Functional Indicators Outcomes
35 The old way of nano risk thinking What is it? Nanomaterial System Descriptors Properties What can happen because of it? Nanoparticle Impacts
36 LEVEL 1 Material and System Properties Shape Size Nanoparticle Properties Composition Coating Amount Product Properties Milieu (solid matrix, suspension ) Availability Release Fraction NOM/ Macromol Ionic Composition ph System Properties Light Surfaces (bacteria, clay ) Fluid Flow Environmental Stressors LEVEL 2 Processes Preceding Biouptake Biodegredation Geochemical Transformations Dissolution Bio-Geo-Chemical Transformations Redox ROS Speciation/ Exposure Potential Aggregation Transport Attachment Settling Deposition Collision Rate Distribution in the System Biouptake / System Transfer LEVEL 3 Processes Following Biouptake Nutrient Cycling Biotransformation Biodistribution LEVEL 4 Outcomes Ecosystem Hazard Trophic Transfer Community Composition Maternal Transfer Cellular and Organismal Hazards LEGEND Parameter or Process Mechanism Example of Mechanism Discovered Via Integrated Research
37 CEINT Structure
38 Currently working with over 50 nanomaterials Citrate-coated Ag nanoparticle potential: -33,0 mv CNTs SWCNTs DWCNTs MWCNTs Caged fullerenes C60 C60(OH) x Quantum dots CdSe ZnS Metal oxides TiO2 CeO2 ZnO FeOx - maghemite - magnetite - hematite Metal sulfides Metals Ag Fe Au surface treatment PVP gum arabic PSS Citrate BSA PAA PEG NOM size 1 to 100 nm shape rod sphere
39 Mesocosms: Exposure and Effects in Complex Real-world Systems 30 mesocosms constructed Probes, data acquisition, and web-based data monitoring Weather, redox conditions, water levels, temp measured continuously
40 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
41 Iterative Feedback Between Field and Lab Scale Experiments mesocosms labs Microcosms in icein TINE wastewater treatment plant
42 Integration Between: People, Disciplines, & Experimental Scales Water Water Water Plants Sediment Water Plants Sediment Ag NPs with different coatings had different effects on DOM release from plants Plant exudates, stimulated by Ag ions, in turn had different effects on Ag NP aggregation and dissolution Via complex interactions, coating type does in fact affect dissolution and therefore toxicity of Ag NPs Bone AJ, Colman BP, Gondikas AP, Newton K, Harrold KH, Unrine JM, et al. Biotic and abiotic interactions in aquatic microcosms determine fate and toxicity of Ag nanoparticles: Part 2 Toxicity and chemical speciation. Environmental Science and Technology 2012; 46: Unrine JM, Colman BP, Bone AJ, Gondikas AP, Matson CW. Biotic and Abiotic Interactions in Aquatic Microcosms Determine Fate and Toxicity of Ag Nanoparticles. Part 1. Aggregation and Dissolution. Environmental Science & Technology 2012; 46:
43 Integration Between: People, Disciplines, & Experimental Scales Dionized Water To investigate environmentally relevant systems, studied effects of rate and extent of Ag NP sulfidation on oxidative dissolution to release Ag ions Showed dramatic decrease in available Ag ions even at low levels of sulfidation Sulfidation (and interaction with chloride) are more important than size in the dissolution behavior of Ag Levard C, Reinsch BC, Michel FM, Oumahi C, Lowry GV, Brown GE. Sulfidation Processes of PVP-Coated Silver Nanoparticles in Aqueous Solution: Impact on Dissolution Rate. Environmental Science & Technology 2011; 45:
44 Partitioning Behavior 889:); 4('+) 6. 7 $ 8.,3%0.92 $!: 0220&+2$;)%&22$<. 9(3$=>. 0+$!"#$ #%&' ( ), $ 123 #%&' ( ) * &+ $./%0).*&+ $!+' $&4$5043 $ $ Wastewater disposal Aggregation Rates Atmospheric deposition. ' /)*%0 &12, %3 4) &% ((?@, $/%(7*. 2 (. /A' *(B. 1' 6%C( Particle Settling Rates ("23+"' </)) 0+%123' 1)!"#$%&'() *+, ( ')./)) 0+%123' 1) 01 $"&#' Surface Water Discharge D1&' E3&' ( )*+,%.*/( 43%55. & &+'6 ' 7%3&/8. %#' 79%. $+9.$#' < =%.> 3)'?8#3@"' 7%3&/:. %; 35. &/' 79%. $+9.$#'!"#$%&'( )$*+" ' *4+2(5) 6%7(+27 ),. /.) */'!"#$%&'()*+)%$,' #. / 0#1)23/ =' /' *. > +: : *' : +3., ( )*+,%7. *2 + 3., %( DG$+3E( H". $ /+I ' ( 0' F 6", : ( Run-off Biosolids Water Column/ Sediment Exchange Atmospheric Deposition!"#$%& '(%#) *&!"##"$%#&'()*+,"() &:;$( <%,&7+18 &1%=*+&0 1>*",?& 41 "&4%1+#5*&!*+,,%*$. *&/ & 012 " %3& 6+#$, 71+8 #91$, & Trophic Transfer Rates. ' /)*%!"#$%&' ()*% +, "#$%&' &'*/'J*+/'( K /+I ' ( 5) 4#2 ),/%3 4) &% 5' 2. &+6(/. (! ' ' ( 0' 1"2 ', /% ( 0' 1"2 ', /+3., (4 (!"#$%"&' () *+, %.*/( )*+,%7. *2 + 3., %( 8' 9: 9(%$6; 1+3.,<(!"#$%"&' () *+, %.*/( Nano-Ag Sulfidation Rates
45 Highlights of Progress to Date Clear Evidence of nanoparticle-specific effects Identification of key parameters controlling spatial and temporal distribution of nanomaterials in the environment Transformations Elaboration of sources and processes generating nanoparticles in natural systems Risk Forecasting
46 How do we Move from this Approach to Making Real Decisions? What decisions must be made? What to regulate What to research next How much information is needed to inform a given decision How much uncertainty we can live with
47 What Should Regulation Address/Prioritize? Hazard or exposure or both? Which material or materials? Greatest use Most potential for release Highest toxicity potential How do we prioritize research to best reduce uncertainty to these questions? Value of information
48 Acknowledgements This material is based upon work supported by the National Science Foundation (NSF)and the Environmental Protection Agency (EPA) under NSF Cooperative Agreement EF , Center for the Environmental Implications of NanoTechnology (CEINT). Any opinions, findings, conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the NSF or the EPA. This work has not been subjected to EPA review and no official endorsement should be inferred. TĪNĒ Mark R. Wiesner, CEINT Director Gregory V. Lowry, CEINT Deputy Director
49 Thank You
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