End-of-life of nano-enabled products by thermal decomposition: Possible environmental health and safety implications
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1 End-of-life of nano-enabled products by thermal decomposition: Possible environmental health and safety implications Georgios A. Sotiriou 1,2, Dilpreet Singh 2, Fang Zhang 2, Lutz Hoering 3, Wendel Wohlleben 2,3, Philip Demokritou 2 1 Department of Microbiology, Tumor and Cell Biology (MTC), Karolinska Institutet, Stockholm, Sweden. 2 Center for Nanotechnology and Nanotoxicology, Department of Environmental Health, T.H. Chan School of Public Health, Harvard University, USA. 3 BASF SE, Material Physics, Germany. georgios.sotiriou@ki.se Visit our lab website:
2 Nanotoxicity: Realistic exposure scenarios? So far: Nanotoxicity evaluation of raw nanomaterials, which is great for: Mechanistic understanding Occupational exposures Realistic exposures? Transformations of nanomaterials during their life-cycle [1] TG3 White Paper Draft, June 1, identify various potential release scenarios for CNT used in polymers and identify the greatest likelihood of release at the various stages throughout the lifecycle of the product and article. [1] Figure 1: Product life cycle of products containing nanoparticles 150 nm [2] The focus of this white paper is on release as a prerequisite for exposure. Exposure is defined as: Contact of an organism with a chemical, radiological, or physical agent. Exposure is quantified as the amount of the agent available at the exchange boundaries of the organism (e.g.; skin, lungs, gut) and available for absorption (source Exposure scenarios are used to describe the conditions that result in exposure, for example the REACH definition of an exposure scenario: Set of conditions, including operational conditions and risk management measures, that describe how the substance is manufactured or used during its life-cycle and how the manufacturer or importer controls, or recommends downstream users to control, exposures of humans and the environment. However, in the context of this white paper, we describe release scenarios and not exposure scenarios. The definition of a release scenario is not unambiguous, however, for the purpose of this white paper a release scenario is defined as the operational and or environmental conditions of any treatment or stress of CNT composite material during all life-cycle phases that results into the release of CNT/composite material into indoor environments, e.g. workplace, dwellings, and or [1] Nowack, David, Fissan, Morris, Shatkin, Stintz, Zepp, Brouwer. Environ. Int. 59, 1 (2013). [2] Pirela, Sotiriou, Bello, Shafer, Bunker, Castranova, Thomas, Demokritou. Nanotoxicology 9, 760 (2015). Georgios A. Sotiriou 22 november
![[1] Wohlleben, Meier, Vogel, Landsiedel, Cox,](/docs-images/79/79303214/images/3-3.jpg "Hirth, Tomovic. Nanoscale 5, 369 (2013).")
3 Knowledge gaps of nano-release at End-of-Life [1] Our TARGET Obtain fundamental understanding on what factors influence the physicochemical and morphological properties of released materials Burning question: Is there a nanofiller-specific effect? [1] Wohlleben, Meier, Vogel, Landsiedel, Cox, Hirth, Tomovic. Nanoscale 5, 369 (2013). Georgios A. Sotiriou 22 november
4 Integrated Exposure Generation System (INEXS) Advantages Figure Versatile: S1. Schematic Easy of to the change Integrated thermal Exposure decomposition Generation System scenario (INEXS) consisting of 3 modules, Real time equipment: Monitor particle concentration, size and composition namely, Collection the incineration of mgof of nano-enabled aerosol: Allows product sufficient under controlled characterization conditions, and the tox post-release studies aerosol In situ inhalation studies: Direct aerosol in animal chambers treatment and the aerosol size-fractionated collection and exposure characterization (both in-situ and ex- Facile collection of residual ash situ). Georgios A. Sotiriou 22 november
5 Umass Lowell BASF MARINA NEPs panel Matrix Polyurethane (PU) Polyethylene (PE) Polycarbonate (PC) Polypropylene (PP) Ethylene vinyl acetate (EVA) nanofiller nanofiller loading application - - carbon black 0.1% (CB) automotive, carbon buildings, textiles nanotubes 0.1% (CNT) - - Fe 2 O 3 1-5% packaging, organic filler 2% buildings, organic filler + constructions 2% UV agent - - automotive, CNT 3% electronics - - packaging, CNT 3% electronics - - packaging, TiO % biomedics Medicinal waste Ag biomedics PU-CNT Georgios A. Sotiriou 22 november
6 Nanofiller effect on aerosol size & concentration? PU-based NEPs Pure and with two different nanofillers (carbon black- CB, and carbon M a x No effect on released aerosol concentration and size due to the nanofiller presence Host polymer dictates the released PM >99% organic carbon, independent of nanofiller presence Georgios A. Sotiriou 22 november
7 Is there any nanofiller in the released aerosol? SEM after dispersion in alcohol and drying on SEM substrate TEM in-situ deposition on TEM grids in CCI PU-CNT (800 C) PM nm PE-Fe 2 O 3 (800 C) PM0.1 PM ICP-MS: wt% Fe PU-CNT 200 nm Georgios A. Sotiriou 22 november
8 Nanofiller effect on chemistry of aerosol? TGA-FTIR (in situ detection of off-gases), ex-situ NMR CO 2, CO and H 2 O, THF, methane, ethylene and aldehydes CO 2, CO and H 2 O, methanol, methane, ethylene, ketones PU-CNT (800 C) PU (800 C) PU (500 C) with I.G. Kavouras, Univ Arkansas Georgios A. Sotiriou 22 november
9 Polycyclic aromatic hydrocarbon (PAH) species 16 Environmental Protection Agency (EPA)-priority polycyclic aromatic hydrocarbon (PAH) species Singh et al., in preparation (2016). with V. Craver, Univ Rhode Island Georgios A. Sotiriou 22 november
10 Is there nanofiller in the residual ash? PU-CNT CNTs in residual ash Homogeneously dispersed throughout the ash 18 times higher concentration than raw NEP 500 C EC (%) OC (%) PU PU-CB PU-CNT Georgios A. Sotiriou 22 november
11 Effect of nanofiller on residual ash composition T d,final = 500 C (PE-Fe 2 O 3 ) Presence of Fe 2 O 3 facilitates full polymer decomposiiton PE-Fe 2 O 3 ICP-MS: 75% wt% Fe 500 C EC (%) OC (%) PE PE-org PE-Fe 2 O Change of Fe 2 O 3 crystal phase for final T = 500 C (reduced from hematite to maghemite) Georgios A. Sotiriou 22 november
12 Summary Novel integrated exposure generation system for the end-of-life thermal decomposition of NEPs Main question: Is there any nanofiller-specific effect? Released aerosol: Not in released aerosol concentration and size Yes in chemical composition Residual ash: Most nanofiller remains in ash Physicochemical properties of remaining nanofiller might not be the same as in raw materials Outlook Collect and extract enough PM for tox studies (in vitro and in vivo) Georgios A. Sotiriou 22 november
13 Acknowledgements HSPH Philip Demokritou Dilpreet Singh Fang Zhang NSF (grant nr ) BASF AG Swiss NSF BASF Wendel Wohlleben Lutz Hoering Univ Arkansas Ilias G. Kavouras Marie-Cecile Chalbot Carnegie Mellon Gregory V. Lowry Eleanor Spielman-Sun Georgios A. Sotiriou 22 november
14 Thank you for listening More info: [1] G. A. Sotiriou, D. Singh, F. Zhang, W. Wohlleben, M-C. G. Chalbot, I. G. Kavouras & P. Demokritou*. An integrated methodology for the assessment of environmental health implications during thermal decomposition of nano-enabled products Environ. Sci.: Nano 2, (2015). [2] G. A. Sotiriou, D. Singh, F. Zhang, M-C. G. Chalbot, L. Hoering, I. G. Kavouras W. Wohlleben & P. Demokritou*. Thermal decomposition of nano-enabled thermoplastics: Possible environmental health and safety implications J. Hazard. Mater. 305, (2016). [3] D. Singh, G. A. Sotiriou, F. Zhang, J. Mead, D. Bello, W. Wohlleben & P. Demokritou*. End-of-life thermal decomposition of nano-enabled polymers: effect of nanofiller loading and polymer matrix on byproducts Environ. Sci.: Nano in press DOI: /C6EN00252H (2016). Open PhD student position in our lab visit: for more info Georgios A. Sotiriou 22 november
15 Georgios A. Sotiriou 22 november
16 Georgios A. Sotiriou 22 november
17 Released aerosol concentration and size (PU-CNT) route 1 (no treatment) T d,final : final thermal decomposition temperature Georgios A. Sotiriou 22 november
18 NANOTOX 2012 G.A. Sotiriou, E. Diaz, M. S. Long, J. Godleski, J. Brain, S.E. Pratsinis, P. Demokritou, A Novel Platform for Pulmonary and Cardiovascular Toxicological Characterization of Inhaled Engineered Nanomaterials, Nanotoxicology 6, (2012).
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26 SMALL 2013 A. Pratsinis, P. Hervella, J-C. Leroux, S.E. Pratsinis, G.A. Sotiriou, Toxicity of Silver Nanoparticles in Macrophages, Small 9, (2013).
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28 [3] Sotiriou, Pratsinis, Environ. Sci. Technol. 44, 5649 (2010).
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39 ACS SUST CHEM 2013 S. Gass, J. Cohen, G. Pyrgiotakis, G.A. Sotiriou, S.E. Pratsinis, P. Demokritou, Safer Formulation Concept for Flame-Generated Engineered Nanomaterials, ACS Sustainable Chem. Eng. 1, (2013).
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46 ES:NANO 2014 G.A. Sotiriou, C. Watson, K.M. Murdaugh, T.H. Darrah, G. Pyrgiotakis, A. Elder, J.D. Brain & P. Demokritou. Engineering Safer-by-Design, Transparent, Silica-coated ZnO Nanorods with Reduced DNA Damage Potential, Environ. Sci.: Nano 1, (2014).
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53 P&FT 2014 N.V. Konduru, K.M. Murdaugh, G.A. Sotiriou, T.C. Donaghey, P. Demokritou, J.D. Brain & R.M. Molina. Bioavailability, distribution and clearance of tracheally-instilled and gavaged uncoated or silicacoated zinc oxide nanoparticles, Part. Fibre Toxicol. 11:44 (2014).
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60 ES:NANO 2015 G. A. Sotiriou, D. Singh, F. Zhang, W. Wohlleben, M-C. G. Chalbot, I. G. Kavouras & P. Demokritou. An integrated methodology for the assessment of environmental health implications during thermal decomposition of nano-enabled products Environ. Sci.: Nano 2, (2015).
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69 NANOTOXICOL OGY 2015 S. Pirela, G.A. Sotiriou, D. Bello, M. Shafer, K. Lee Bunker, V. Castranova, T. Thomas & P. Demokritou. Consumer exposures to laser printer-emitted nanoparticles: A case study of the life-cycle implications from nano-enabled products Nanotoxicology 9, (2015).
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