Engineered Nanomaterials in the Energy Sector: Preparing for an Emerging Occupational Hazard EPRI 2nd Annual Occupational Health & Safety Meeting Conference May 19, 2015 Gregory Nichols, MPH, CPH Program Manager, Nanotechnology Studies, ORAU

Definitions Nanotechnology is the intentional manipulation of matter On an atomic scale (1-100 nm) To make new structures/materials Engineered nanomaterials Have unique properties that make them Useful And dangerous

Scale of Nanomaterials Yokel and MacPhail, J Occ Med and Tox, 2011

Properties of Nanomaterials Change in optical properties Change in electrical properties Change in physical properties (i.e., melting point) Increased mechanical strength Quantum effects http://www.wattagnet.com/How_to_manage_feed_mill_safety_when_mixing_nano-sized_powders.html

Types of Engineered Nanomaterials Nanomaterial Category Features and Types Example Products Fullerenes C60, carbon nanotubes, graphene Conductive films, fuel cells, composites, cosmetics Ceramics Iron oxides, titanium dioxide Photocatalysts, magnetic data storage, coatings, sun-screens, paint Metals Silver, gold, platinum Antomicrobial fabrics, oxidation catalysts, sensor elements Quantum dots Cadmium chalcogenides Solar cells, diodes, biologic markers Polymers Copolymer assemblies, dendrimers Coatings, rheologic control, drug delivery NAS, A Research Strategy for EH&S Aspects of Eng Nanoparticles, 2012

Applications of Nanotechnology in the Energy Sector Hessian Ministry of Economy, Transport, Urban and Regional Development, 2008

Current State of Nano in the Energy Sector Processes Maintenance Production/Manufacturing Materials Lubricants Paints and coatings Photovoltaic cells Electronic components Batteries Turbines/Blades

Potential for Exposure State of the nanomaterial Employee activity Potential exposure source Bound or fixed nanostructures (polymer matrix) Grinding, etching, erosion, abrasion, sanding, drilling, heating, cooling Release during grinding, drilling, and sanding; Damage to matrix Liquid suspension, dispersion Synthesis methods; Pouring/mixing liquids; Sonication; Spraying Aerosolization of nanoparticles during sonication or spraying Dry dispersible nanomaterials and agglomerates Collecting materials, weighing powders, mixing powders Exposures while handling dry powders Nanoaerosols and gas phase synthesis Vapor deposition, vapor condensation, spraying Direct leakage from reactor, processing and packaging dry powder, cleaning equipment, maintenance NIOSH, Gen Safe Practices for Working with Eng Nanomaterials in Research Labs, 2012

Routes of Entry/Exposure Pathways Oberdorster, Env Health Perspectives, 2005

Actions of Nanomaterials http://blogs.rsc.org/en/2014/03/24/the-bioavailability-of-nanomaterials-in-the-aquatic-environment/

Analysis of a DOE Worker Cohort Definition of a “nano” worker (DOE O 456.1) Has the potential for inhalation or dermal exposure to unbound engineered nanoparticles Routinely spends time in an area in which engineered unbound engineered nanoparticles have the potential to become dispersed in the air or on surfaces; or Works on equipment that might contain or bear unbound engineered nanoparticles and that could release unbound engineered nanoparticles during servicing or maintenance.

Analysis of a DOE Worker Cohort (cont’d) Illness and Injury Surveillance Program (IISP) Monitored 125,000 workers 14 DOE Sites Nearly 20 years 759 nano-workers (2008-2011) (51,000 total workers) BNL, Hanford, INL, LLNL, ORNL 1.5% of samples population Female – 20%, Male – 80% Field Professionals, In-house Professionals Respiratory diagnosis the highest No difference in absences, or number of diagnoses

Liou et al, J Nanopart Res, 2012 Cross-sectional study 14 facilities in Taiwan 364 workers (227 handled nano, 137 did not) Mixed exposure (CNT, Si, TiO2, nanometals) CVD markers increased in nano group (fibrinogen, IAM-1, IL-6)

Worker Registries BASF (2009 - ) France (2013 - ) Challenges North America (210 sites, 11,000 workers) 5% of all BASF sites use nanomaterials France (2013 - ) Multiple types of production facilities Carbon nanotubes, titanium dioxide Challenges Definition of “nanoparticles” Most exposures are compound Limitations on measurement technologies Most workers are in mfg or chemicals Small sample size

Exposure Scenarios and Engineering Controls State of the nanomaterial Employee activity Potential exposure source Recommended engineering controls Bound or fixed nanostructures (polymer matrix) Grinding, etching, erosion, abrasion, sanding, drilling, heating, cooling Release during grinding, drilling, and sanding; Damage to matrix LEV Lab chemical hood (HEPA) Glovebox (HEPA) Bio safety cabinet class II Liquid suspension, dispersion Synthesis methods; Pouring/mixing liquids; Sonication; Spraying Aerosolization of nanoparticles during sonication or spraying Dry dispersible nanomaterials and agglomerates Collecting materials, weighing powders, mixing powders Exposures while handling dry powders Nanoaerosols and gas phase synthesis Vapor deposition, vapor condensation, spraying Direct leakage from reactor, processing and packaging dry powder, cleaning equipment, maintenance Glovebox or other sealed enclosure with HEPA Equipment for monitoring toxic gases NIOSH, Gen Safe Practices for Working with Eng Nanomaterials in Research Labs, 2012

Administrative Controls/PPE Awareness Training Communication Personal Protective Equipment Respirators OSHA Respiratory Protection Standard Follow NIOSH Respirator Selection Logic (N 95) Double-gloved (nitrile, latex, neoprene) Non-woven textiles (high-density polyethylene); disposable preferred Medical screening and surveillance Biological monitoring

Regulations (Sort of) Category Agency Legislation Occupational Health and Safety Department of Labor/Occupational Safety and Health Administration American Conference of Governmental Industrial Hygienists National Institute for Occupational Safety and Health Occupational Safety and Health Act, 29 U.S.C. § 651 (1970) Threshold Limit Values for Chemical Substances Committee studying “primary particle notation” Recommended Exposure Limit (REL) CNT - 1µg/m3 TiO2 – 0.3mg/m3 Industrial Chemicals Environmental Protection Agency Toxic Substances Control Act, 15 U.S.C. § 2601 (1976) Section 8(a) SNUR Environment Clean Water Act, 33 U.S.C. § 1251 (1977) Resource Conservation and Recovery Act, 42 U.S.C. § 6901 (1976) Clean Air Act, 42 U.S.C. § 7401 (1970) Bowman and Hodge, Columbia S&T Law Review, 2007

Knowledge Gaps in Nanomaterial Work Places Hazard Identification Toxicologic research Health effects assessment Safety research Hazard Characterization Field assessment Epidemiologic and hazard surveillance research Exposure Assessment Metrology research Control technology research Personal protective equipment research Risk Characterization Risk assessment Dose-response modelling Exposure characterization Epidemiologic research Risk Management Risk communication Guidance development for controls, exposure limits, PPE, and medical surveillance Information dissemination Adherence investigation NIOSH, Protecting the Nanotechnology Workforce, 2013

The Nichols Method for Dealing With Nano Identify – Processes/materials with nano Evaluate – Current practices Assess – Adequacy of controls based on current guidelines Adjust – Change based on science/recommendations/practicality Communicate – Risk, mission, and measures