Nano-Sized Particles in the Environment: Fate, Transport and Potential Impacts to Ecosystem Health

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1 Nano-Sized Particles in the Environment: Fate, Transport and Potential Impacts to Ecosystem Health National Academies Workshop on Challenges in Characterizing Small Particles: Exploring Particles from the Nano- to Microscales Washington, D.C. 25 October 2010 Pedro J.J. Alvarez CBEN

2 Growth of Nano-Related Publications (3-year doubling time) Source: Web of Science

3 Microbial-nanoparticle Interactions to Inform Risk Assessment Bacteria are at the foundation of all ecosystems, and carry out many ecosystem services Disposal/discharge can disrupt primary productivity, nutrient cycles, biodegradation, agriculture, etc. Antibacterial activity may be fast-screening indicator of toxicity to higher level organisms (microbial sentinels?) 3

4 Bacterial Toxicity Mechanisms Release of toxic ions by QDs, nano-silver, nzno Cd 2+ Zn 2+ Ag + Protein oxidation Disruption of membrane/ cell wall by carboxyfullerene DNA damage e - ROS Interruption of respiration and protein oxidation upon contact (e.g., nc 60,CeO 2 ) e - Generation of Reactive Oxygen Species by TiO 2 & aminofullerenes

5 Nanoparticle Modifications in the Environment Alvarez P.J.J., V. Colvin, J. Lead and V. Stone (2009). Research Priorities to Advance Eco-Responsible Nanotechnology. ACS Nano 3(7):

6 Salts promote coagulation & precipitation = less toxicity 160 Mean n Particle Diameter (nm) Ionic Strength of Fresh Water Seawater 0.7M Smaller = less toxic >100 nm <100 nm B. subtilis MIC (mg/l) Ionic Strength (M, NaCl)

7 Dry 14 C 60 Bioaccumulation in Earth Worms Lower BASF at higher C 60 concentration (no avoidance) 0.06 mg/g 0.10 mg/g 0.30 mg/g Eisenia fetida Epigeic worm Lives at or near the surface Consumes surface litter and soil organic matter Sexually mature weight g Bioaccumulation factor: BASF = 14 C in worm/ 14 C in soil Soil NOM had little effect on BASF Higher BASF for (smaller) phenanthrene despite its lower K ow 0.3% 0.7% 5% % organic carbon in soil Li D., J.D. Fortner, D.R. Johnson, C. Chen, Q. Li and P.J.J. Alvarez (2010). Environ. Sci. Technol. (In press)

8 NOM reduces bioavailability & toxicity of nc 60 Cumulative CO 2 production (μmole) nc 60 -free control 100 mg soil+nc 60 nc 60 only 92 mg sand+nc mg humic acid+nc 60 nc 60 trapped by humic colloids 200 nm nc Time (h) Humic acid concentrations as low as 0.1 mg/l eliminated toxicity Li, D., Lyon D.Y., Q. Li, and P.J.J. Alvarez (2008). Environ. Toxicol. Chem. 27(9):

9 Coating NZVI Decreases Direct Contact and Toxicity, Enabling Expression of Dehalogenase Genes in Dehalococcoides spp. (Enables Microbial Reductive Dechlorination) Uncoated nzvi: downregulated Poly-peptide Coated nzvi: upregulated Log 10 (gene expression fold changes) (a) Time (h) tcea vcra Log 10 (gene expression fold changes) (b) Time (h) tcea vcra Xiu Z-M, K.B. Gregory, G.V. Lowry, and P.J.J. Alvarez (2010). Environ. Sci. Technol. (In Press).

10 Dissolved NOM Enhances C 60 Dispersion Dispersed C 60 was measured as dissolved TOC C 60 + DI C 60 + SRHA SRHA C 60 + SRFA SRFA 5 C 60 concentration (mg/l) mg/l SRHA 10 mg/l SRHA 5 mg/l SRHA 1 mm NaCl No HA after 72 hr Mixing time (hr) Li, Q. et al., ES&T, 2009, 43(10):

11 Dissolved NOM Decreases nc 60 Deposition onto a Quartz Surface, Increases Mobility in Water Quartz Crystal Micro Balance Depositing Nanoparticles Oscillating quartz crystal detector ~ Mass Deposition Rate dm/dt (ng hr -1 ) mm Ca, HA 15 mm Ca, FA 10 mm Ca, HA 10 mm Ca, FA NOM Concentration (mg/l)

12 Risk = Hazard Exposure Hazard, but no exposure Exposure but no hazard Hazard as well as exposure

13 Synthetic Nanoparticles in Natural Water Example manufactured nanoparticles/ml 10 8 natural nanoparticles/ml (erosion, eruptions, combustion, etc)

14 We Need to Quantify MNM Sources Better What are the main entry points and scale of discharges into the various environmental compartments? What form is being discharged where and how much? What are realistic environmental relevant exposures? Inventory the production and use of NPs within defined spatial domains (voluntary/regulatory disclosure). Determine typical NP waste production patterns (including leaching from products that incorporate NPs) Temporal and spatial multimedia sampling of likely release and exposure sites (include new analytical and biologic indicators of exposure).

15 International Workshop on Priorities to Advance the Eco-Responsible Design and Disposal of ENMs (Rice University, March 9-10, 2009) What critical knowledge gaps and opportunities exist to inform and advance the design of environmentally benign ENMs and the management of wastes containing them?

16 Towards Ecoresponsible Nanotechnology (high) Relative Importance Most urgent priorities Metrology & analytical methods To track ENMs and validate models Structure-activity relations to predict toxicity, speciation & fate Bioavailability & bioaccumulation Trophic transfer & biomagnification Issues that may gain importance Inventory and quantification of sources & environmental fluxes (e.g., rate of leaching from material) Uptake mechanisms Intra-organism NP distribution, bioconcentration, and fate Important issues to tackle Predictive models of release & exposure scenarios Dose response (sublethal) Identification of relevant sentinel organisms Lower research priorities Impact on environmental protection infrastructure (landfills, water and wastewater treatment plants, etc.) Assessing regulatory framework & classification of NM for disposal Assessing regulatory framework for waste minimization & recycling (low) (low) Relative State of Knowledge (high) Alvarez P.J.J., V. Colvin, J. Lead and V. Stone (2009). Research Priorities to Advance Eco-Responsible Nanotechnology. ACS Nano 3(7):

17 Conclusions Implications: Ecotoxicology- Ecosystem services (primary productivity, food webs, nutrient cycling?) biodiversity? Toxicity to higher organisms? Mitigated by NOM, salts Applications: DBP-free disinfection, advanced (photo) oxidation processes, antifouling/corrosion coatings? functionalized membranes

18 Any Questions?

19 Backup Slides

20 The 12 Principles of Green Nanotechnology 1. Inherent rather than circumstantial (use raw materials and elements that are inherently non-hazardous if released) 2. Prevention rather than treatment (containment, minimize exposure, design away hazardous functionalities or features without impacting useful functions?) 3. Design for separation and purification of wastes (take advantage of magnetic properties for separation? Stabilizing coatings that can be intentionally removed?) 4. Maximize mass, energy, space and time efficiency (multi- functionality of NPs may be desirable) 5. Out-pulled rather than input-pushed through the use of energy and materials (quality > quantity, need > greed, enough > more, long-term > short-term) term)

21 The 12 Principles (Continued) 6. Find opportunities for recycle, reuse or beneficial disposition (non toxic NPs that enhance nutrient or water retention and soil fertility?) 7. Target durability rather than immortality (pick the right coatings, avoid indefinite persistence) 8. Need rather than excess - don t t design for unnecessary capacity avoid one size fits all (incorporate just what you need, avoid excess MNMs in commercial products) 9. Minimize material diversity to strive for material unification and promote disassembly + value retention (take advantage of economy of scales, minimize variability and sources of a given MNM?)

22 The 12 Principles (Continued) 10. Integrate local material and energy flows (holistic LCA perspective, look for interconnectivity, system of systems) 11. Design for commercial afterlife (enable recycling, remanufacturing and/or reuse opportunities? beneficial disposition?) 12. Use renewable & readily available inputs through life cycle (minimize carbon, land use and water footprint?)

23 Decrease in B. subtilis membrane potential Red/Green Ratio Antibacterial Mechanisms of nc nc 60 exerts ROS-independent 0.25 oxidative stress, with evidence of 0.20 protein oxidation, collapse of 0.15 membrane potential, and interruption of cellular respiration & energy transduction t-booh nc 60 control nc 60 CCCP nmoles thiol in BSA Percent of Respiring Cells Protein Oxidation (thiol loss) (+ control) -Control Decrease in E. coli respiration -Control nc 60 Azide (+ control) Lyon D.Y., L. Brunet, G.W. Hinkal, M.R. Wiesner, and P.J.J. Alvarez (2008). Nanoletters. 8(5): Lyon & Alvarez (2008). ES&T. 42:

24 Toxicity of common nanomaterials to bacteria Increasing toxicity MIC (ppm) THF/nC 60 son/nc 60 aq/nc 60 PVP/nC 60 Ag + nano-ag NaOCl nzno nzvi ntio 2 (sunlight) nsio 2

25 Facilitated Transport of contaminants by nc 60 in soil PCB Straining PCB+ Soil particles Soil OM Deposition Adsorption Co-transport Soil water Sorption HOCs are co-transported with nc 60 (none detected without nc 60 )

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