Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia) 1

Outline 1.Introduction to nanotechnology 2.Work health and safety legislation 3.Applying the work health and safety legislation to nanomaterials 4.Nanomaterial hazards 5.Eliminating or minimising exposure to nanomaterials 6.Measuring and assessing exposure to nanomaterials 7.Nanowaste 8.Safe Work Australia’s Nanotechnology Work Health & Safety Program 2

Acknowledgements Information on some of the slides is from the draft Nanotechnology WHS Training Course developed by RMIT School of Applied Sciences for Safe Work Australia Dr Neale Jackson, Project Team Leader Ms Lisa Stevens Ms Carole Goldsmith Mr Stephen Thomas Funding provided by Department of Industry, Innovation, Science, Research and Tertiary Education under the National Enabling Technologies Strategy 3

INTRODUCTION TO NANOTECHNOLOGY 4

Nanotechnology - Definitions nanotechnology (ISO TS :2010 Core terms) application of scientific knowledge to manipulate and control matter in the nanoscale in order to make use of size- and structure-dependent properties and phenomena, as distinct from those associated with individual atoms or molecules or with bulk materials nanoscale (ISO TS 27687) size range from approximately 1 nm to 100 nm nano-object (ISO TS 27687) material with one, two or three external dimensions in the nanoscale –one dimension (nanoplates) –two dimensions (nanorods, nanotubes, nanowires) –three dimensions (nanoparticles) 5

About Nanomaterials nanomaterial definition (ISO TS 80004:1) material with any external dimension in the nanoscale or having internal structure or surface structure in the nanoscale Nanomaterials can exist: – as primary particles – as aggregated or agglomerated forms – in a range of regular or irregular shapes NICNAS working definition of Industrial Nanomaterials Industrial materials intentionally produced, manufactured or engineered to have unique properties or specific composition at the nanoscale, that is a size range typically between 1 nm and 100 nm, and is either a nano-object (ie. that is confined in one, two, or three dimensions at the nanoscale) or is nanostructured (ie. having an internal or surface structure at the nanoscale) 6 Agglomeration signifies more loosely bound particles and Aggregation signifies very tightly bound or fused particles

Particle Size Comparison Animal, plant or fungi membrane cells

Different Types of Nanomaterials Naturally Occurring Human Origin (Incidental) Human Origin (Engineered/ Manufactured) Forest firesCooking smokeMetals Sea sprayDiesel exhaustQuantum dots Mineral compositesWelding fumesNanotubes & Nanowires Volcanic ashIndustrial effluentsMetal oxides VirusesSandblastingFullerenes Nanotechnology Adapted from: Lippy and Kulinowski 8

Properties Can Change at the Nanoscale Nanomaterials can have – unique or enhanced physical & chemical properties – different biological & toxicological behaviour Properties that can change include: Colour Chemical reactivity Electrical conductivity Magnetism Mechanical strength 9

Red Gold Nano Gold = Red Loses conductivity at ~ 1-3 nm Becomes magnetic ~ 3 nm Explosive and catalytic Gold (~ 10 nm) Bulk Gold (Au) = Yellow Conductive Nonmagnetic Chemically inert 16 nm gold National Measurement Institute,(NMI) Australia Source: Lippy and Kulinowski 11

Nanotechnology in Australia Areas such as nanomaterials, nano-biotechnology, electronics, photonics, energy, environment, quantum technology More than 75 nanotechnology research organisations and around 80 nanotechnology companies Products include: –Dyesol’s dye solar cell –SonoEye™ from Seagull Technologies, uses a combination of nanotechnology and ultrasound to replace injections to the eye –TenasiTech’s high performance composite polymers –Sunscreens –CAP-XX’s high power and energy density supercapacitors Sources: Australian Innovation System Report 2011, DIISRTE website 13

Nano-Enabled Glasses Glasses –Self cleaning glass –Low reflective glass –Switchable glass Source: AccessNano (adapted) self cleaning normalglass 14 OptiView TM Low reflective glass Made by Pilkington

Detecting Cancer Cells Breast Cancer Res Treat (2010) 120:547–555 with nanoshells without nanoshells normalHER2- cancer HER2+ cancer without nanoshells with nanoshells Small silica sphere with thin gold coating Enhances the detection of cancer cells in real time Why nanoparticles? Gold plated nanoparticles visible to imaging process 13

Nanomaterials - Manufacturing Key characteristics of nanoparticles Particle size, size distribution, shape, composition Degree of particle agglomeration Nanomaterial production methods Bottom up & top down methods Solid, liquid & gas phase synthesis Milling & grinding Precipitation Vapour phase reactions 14

WORK HEALTH AND SAFETY LEGISLATION 15

16 Model WHS Legislation Council of Australia Governments formally committed to harmonisation of WHS laws (July 2008) Model work health and safety legislation: –model Work Health and Safety (WHS) Act –model Work Health and Safety (WHS) Regulations –model Codes of Practice –National Compliance and Enforcement Policy –supported by guidance material Developed by Safe Work Australia –Partnership of Commonwealth, state & territory governments, ACTU (representing workers), ACCI & AIG (representing employers)

17 Model WHS Legislation - Implementation New WHS laws commenced in NSW, Queensland, ACT, Commonwealth and Northern Territory, 1 January 2012 New laws commenced in South Australia & Tasmania on 1 January 2013

18 Model WHS Legislation – Duty Holders Person conducting a business or undertaking (PCBU) –Persons who have management or control of a workplace –Manufacturers –Importers –Suppliers –Designers Officers Workers

19 WHS Regulations - Managing Risks Duty to identify hazards A duty holder must identify reasonably foreseeable hazards that could give rise to risks to health and safety Managing risks to health and safety A duty holder must: (a)eliminate risks to health and safety so far as is reasonably practicable (b)if it is not reasonably practicable to eliminate risks to health and safety — minimise those risks so far as is reasonably practicable Code of Practice - How to Manage Work Health and Safety Risks

Reasonably Practicable What is reasonably able to be done to ensure health and safety, taking into account all relevant matters including: the likelihood of the hazard or the risk occurring the degree of harm that might result availability & suitability of ways to eliminate or minimise the risk what a person ought reasonably to know about the hazard or risk and how to eliminate or minimise the risk cost associated with eliminating or minimising the risk 20

21 Duties of Designers Model WHS Act, Section 22 Duties apply to the designer - the PCBU that designs plant, substance or structure for workplace use Designer must ensure, so far as is reasonably practicable, that the plant, substance or structure is designed to be without risks to the health and safety of persons Duties involve, where necessary: –calculations, analysis, testing or examination –giving adequate information to each person who is provided with the design

WHS Regulations for Workplace Chemicals 22 Manufacturer or importer must: −determine whether a substance is a hazardous chemical −if it is, prepare a safety data sheet and correct label Hazard classification is according to the GHS Supplier of a hazardous chemical to a workplace must ensure that the current safety data sheet for the chemical is provided PCBU must ensure that hazards in relation to using, handling or storing a chemical at the workplace are identified, and the associated risk is eliminated or minimised so far as is reasonably practicable.

APPLYING THE WORK HEALTH AND SAFETY LEGISLATION TO NANOMATERIALS 23

24 Application of Work Health and Safety Regulatory Framework to Nanotechnologies Obligations under work health and safety legislation need to be met for nanomaterials and nanotechnologies Where understanding of nanomaterial hazards is limited –use precautionary approach to prevent or minimise workplace exposures to manufactured nanomaterials Workplaces can have a number of hazardous chemicals Engineered nanomaterials & other chemicals Controls used must be appropriate for both Chosen based on hazards of nanomaterials and other chemicals in the workplace

25 Taking a Precautionary Approach There are a number of possible approaches if there is only a limited understanding nanomaterial hazards e.g: Approach 1 By considering what would be a reasonable worst case, determine how severe the hazard could be Choose controls that are appropriate for that hazard severity Approach 2 Assume nanomaterials are highly hazardous Implement high level engineering controls – enclosure or isolation Approach 3 Identify controls used for the same/similar process with larger particles Use more stringent controls for nanomaterials –e.g. if general ventilation is used for larger particles, use LEV for nanomaterials

26 Supporting Regulation SDS & Workplace Labelling Safety Data Sheets (SDS) and workplace labels must be provided if chemical classified as hazardous –Many engineered & manufactured nanomaterials are not currently classified –Issues with SDS & labels for nanomaterials (J.Frangos, Toxikos 2010) Model Codes of Practice for SDS & Workplace Labelling –Recommend SDS/label should be provided for engineered or manufactured nanomaterials unless evidence they are not hazardous International work on SDS & nanomaterials –ISO Technical Report: Preparation of safety data sheets for manufactured nanomaterials –UN Sub-Committee of Experts on the GHS

NANOMATERIAL HAZARDS 27

Health impacts of emissions containing incidental nanoparticles Human Origin (Incidental) Health Impacts Cooking smoke Pneumonia; chronic respiratory disease; lung cancer Diesel exhaust Cancer; respiratory disease IARC classified diesel engine exhaust as carcinogenic to humans (2012) Welding fumesMetal fume fever; infertility; benign pneumoconiosis SandblastingSilicosis Adapted from: Drs Lippy and Kulinowski 28 Considerable knowledge on health impacts of fine & ultrafine particulate air pollution

29 Health Hazards – Factors that Impact on Toxicity Original toxicity of bulk material Size (within the nanoscale range) Surface area Shape, aspect ratio & length Solubility Surface coating Biopersistence Agglomeration state

Exposure Pathway Model Process Work surfaces SkinIngestion Inhalation Skin absorption Air 38 Source: Drs Lippy and Kulinowski, from Mulhausen and Damiano

Workplace - Main Concern is Exposure by Inhalation Airborne nanoparticles can be inhaled and deposit in the respiratory tract Inhaled nanoparticles may enter the blood stream and translocate to other organs Nanoparticle penetration into the lung depends on its size, e.g. on its agglomeration state Image: Source: Drs Lippy and Kulinowski 31

32 Particle Toxicity Particle exposure Normal clearance No adverse effect Low dose Prolonged stress (oxidative) Cell Repair & Removal (Macrophage) High dose Inflammatory cell recruitment (Cytokines) Growth factors cell proliferation (Epithelial) Cell transformation Genotoxicity Mutations Cell damage Proliferation of fibroblasts Lung Fibrosis Lung Cancer Inflammatory response Source:

33 Fibre Toxicity Fibre exposure Deposition Short Fibre Effective removal (phagocytosis & macrophage) No adverse effect Breaks Long Fibre Non-biopersistant Dissolves Biopersistant Incomplete removal (phagocytosis) Prolonged inflammation Fibrosis Granuloma Cancer (mesothelioma) Source:

34 Health Hazards – Inhalation hazards Range of hazard severities Can have: –Particle toxicity –Fibre toxicity Nanoparticles generally more toxic than larger particles of same material Total particle surface area better predictor of toxicity than mass dose Animal studies have indicated: –nanoparticles may induce cancers in rodents, including mesothelioma from biopersistent fibre-like nanomaterials –formation of rapid and persistent pulmonary fibrosis Alveolar Epithelial Penetration by Multi-walled Carbon Nanotube Courtesy of R. Mercer, NIOSH

Dermal Exposure Several studies show little or no penetration of nanoscale oxides beyond surface skin layers, e.g.: Small amounts of zinc from zinc oxide particles in sunscreens applied outdoors are absorbed through human skin. Toxicol Sci Nov;118(1): B.Gulson, M.McCall et al Skin cannot be ruled out as a potential route of exposure 35

36 Health Hazards of Carbon Nanotubes Potentially hazardous if fibre-like, but also if not fibre-like Durability of carbon nanotubes and their potential to cause inflammation (M. Osmond et al, CSIRO/IOM/Edinburgh University 2011) –Carbon nanotubes can be durable but may break down in simulated lung fluid, depending on sample type –If fibre-like and sufficiently long, carbon nanotubes can induce asbestos-like responses in the peritoneal cavity of mice, but this response is significantly reduced if nanotubes are less durable –Tightly agglomerated particle-like bundles of carbon nanotubes did not cause an inflammatory response in the peritoneal cavity of mice

37 Human Health Hazard Assessment & Classification of Carbon Nanotubes Classification undertaken by NICNAS (2012) according to both: –3rd Revised Edition of the GHS –Approved criteria for classifying hazardous substances being replaced by the GHS criteria may still be used during the regulatory transition period Summary of the recommended GHS classifications by NICNAS Classification recommended Health Hazard End Point Classified as hazardous Carcinogenicity: Category 2 Specific target organ toxicity - repeated exposure: Category 2 Not classified as hazardous Acute toxicity: Oral, Dermal Serious eye irritation Skin irritation Skin sensitisation Specific target organ toxicity - single exposure Cannot be classified Acute toxicity: Inhalation Respiratory sensitisation Germ cell mutagenicity Reproductive toxicity

38 Laser Printer Emissions Measured as Particles Based on exposures measured in Laser printer emissions in workplace environments (P.McGarry et al, QUT/WHSQ 2011) –Majority of nanoparticle exposure experienced by workers did not come from printers but from other sources –Considered emissions measured as particles Comparison of laser printer particle emissions with Australian & international benchmarks Risk of direct toxicity and health effects from exposure to laser printer particle emissions for most people is negligible, but people responsive to unusual or unexpected odours may detect and react to the presence of emissions A brief review of health effects of laser printer emissions (R.Drew, Toxikos 2011)

Emissions from composites & other solid articles during machining Quantity of emissions not significantly affected by presence of nanomaterials High energy machining processes emit significantly higher numbers of particles Lower emissions can be achieved using wet machining in place of dry machining Mixture of particles is released from composites –mostly from matrix 2 studies reported emission of free carbon nanotubes & nanofibres - other machining studies did not detect the emission of free carbon nanotubes Investigating the emissions of nanomaterials from composites and other solid articles during machining processes, CSIRO 2013

Potential health risk from emissions Unless reinforcing nano-objects are of high toxicity, similar health risk from machining of composites with/without reinforcing nano-objects Potential health risk from high energy machining processes Levels of emissions from low energy process should not present a significant health risk, unless emitted particles have high toxicity Investigating the emissions of nanomaterials from composites and other solid articles during machining processes, CSIRO 2013

Safety Hazards of Nanomaterials Accidental explosions involving metal nanopowders have resulted in deaths of workers –during production of aluminium nanopowder by mechanical attrition milling –in premix plant of a slurry explosive factory when loading a batch mixer with very fine aluminium flake Dust clouds of a some types of engineered nanomaterials can result in very strong explosions if –concentrations of engineered nanomaterials in air are sufficiently high, and –dusts can be ignited Severity of explosion for engineered nanomaterials no higher than for micron-sized counterparts Evaluation of potential safety (physicochemical) hazards associated with the use of engineered nanomaterials (Toxikos 2013)

Evaluation of potential safety hazards Minimum explosive concentration (MEC) is significantly higher (30-70g/m 3 ) than found in a well-managed workplace as a result of fugitive emissions from nanotechnology processes In some situations where production is not designed and/or controlled effectively, air concentrations in localised areas may be sufficiently high to result in explosions Minimum ignition energy (MIE) varies with material type –Nanoscale metal powders are easily ignited (low MIE, <10mJ) –Carbon nanomaterials are not easily ignited (high MIE, >1000mJ) Evaluation of potential safety (physicochemical) hazards associated with the use of engineered nanomaterials (Toxikos 2013)

ELIMINATING OR MINIMISING EXPOSURE TO NANOMATERIALS 43

44 RMIT University©2010 NanoSafe Australia 44 Likelihood of Nanoparticle Exposure in the Workplace Material & application dependent Potentially highest when handling free particles –Transfer of nanomaterials in open systems –Cleaning of “dust” collection systems –Equipment maintenance –Clean-up of spilled nanomaterials Lower when –Working with articles containing embedded nanoparticles –During manufacturing in enclosed systems

45 Workplace Controls for Nanomaterials Control of exposure –conventional controls can effectively reduce exposures –apply the hierarchy of control N. Jackson et al, RMIT University 2009 Use of PPE when working in fume cabinet with engineered nanomaterials (CSIRO, 2009)

46 Level 2 – Substitution & Modification Substitution more likely than elimination Issue – maintaining product properties C. Sayes et al. (2004) Nano Letters 4(10):

Level 2 - Isolation Controls Good evidence of successful application in several situations/scenarios Gloveboxes are a type of isolation being used for handling nanoparticles Nanomaterial testing. Photo courtesy EPI Services, Inc 47

48 Effectiveness of Engineering Controls Number of CNTs/cm 3 Before process enclosure After process enclosure Personal Area Process enclosure Blending with carbon nanotubes for composites. (Han et al, Inhalation Toxicology, 2008) LEV Effectiveness From McGarry et al (QUT/WHSQ 2012)

49 RMIT University©2010 NanoSafe Australia 49 Nanoparticle Filtration Fibrous filters are efficient for capturing nanoparticles For Particles >1000 nm –Interception (collision with fibre) –Inertia (don’t deviate with air flow around fibre) For Particles <100 nm (nanoparticles) –Diffusion (Brownian motion enhances collision) Max Penetrating Particle Size (MPPS) nm (EU Nanosafe2, Jan 2008 )

50 Level 3 – Administrative Controls Used to supplement engineering controls Some nanomaterial-specific practices –Sticky mats at room entrances to prevent transfer by foot –Routine maintenance & clean-up of work areas, clean-up of spills wet wiping & vacuum cleaning, dry wipe for liquid spills only use of respirators & dermal protection –Waste disposal (nanomaterials & used PPE, wipes, equipment ) separate disposal containers recycling nanomaterials incinerating waste nanomaterials on-site (carbonaceous) returning nanomaterials to suppliers ISO TR 12855: Health and safety practices in occupational settings relevant to nanotechnologies (2008)

Level 3 – Personal Protective Equipment (PPE) 51 Used to supplement engineering controls Gloves Nitrile (most generally used), Neoprene, Polyvinyl chloride (PVC), Latex Single/Double gloving Protective Clothing Eye Protection Face shields, Safety glasses, Goggles Masks Full or half respirators - P2 & P3 type masks, Dust masks

52 Control of Safety Hazards Same principles that apply to management of fine powders, dusts & dusty materials should be considered –Avoid dust becoming airborne –Handling combustible nanopowders in liquid form when possible –Design of machinery to prevent ignitions and sparks control operating temperature of electrical equipment –Use of controlled-atmosphere production and storage processes risk of asphyxiation

MEASURING & ASSESSING EXPOSURE TO NANOMATERIALS 53

54 Measuring Workplace Exposures & Emissions of Manufactured Nanomaterials Measurement challenges –Many different types –Tend to agglomerate –Background nanoparticles Which parameters to measure? –mass concentration –number concentration –size distribution –shape and chemistry –surface area Size distributions of Pt particles after release in a clean exposure chamber. NANOTRANSPORT (2008): The Behaviour of Aerosols Released to Ambient Air from Nanoparticle Manufacturing

55 Approach for Workplace Measurement 3-tiered approach can be used Tier 1 assessment - standard occupational hygiene survey of process area & measurements to identify likely points of particle emission Tier 2 assessment - measuring particle number and mass concentration to evaluate emission sources & workers’ breathing zone exposures Tier 3 assessment - repeat Tier 2 measurements & simultaneous collection of particles for off-line analysis Measurements of Particle Emissions from Nanotechnology Processes, with Assessment of Measuring Techniques and Workplace Controls (P.McGarry et al, QUT/WHSQ, 2012)

56 Measurement of Nanoparticle Emissions Research set-up for measurement of nanoparticle emissions (P.McGarry et al, QUT/WHSQ, 2012 ) Combination of P-Trak, DustTrak & OPC sufficient for workplace investigations

57 Exposure Standards

NANOWASTE 58

Nanomaterials Waste Streams Manufactured nanomaterials Nano by-products, organic or inorganic Liquid suspensions containing nanomaterials Items contaminated with nanomaterials (e.g. wipes/PPE). Solid matrices containing nanomaterials. Also need to deal with: Spills & accidental releases 59 orkshop-Houston-Texas(FINAL).ppt

Potential Approaches for Handling Nanowaste Reuse/recycle – cost of material promotes conservation - may require separation or segregation of nanomaterials and nanoproducts Acid dissolution of metals High ‐ temperature incineration of organic nanomaterials Sintering of ceramics or oxides Long-term storage for inorganics Landfill General waste handling regulations apply for handling nanowaste in Australia - currently there are no nanowaste-specific regulations in Australia 60

SAFE WORK AUSTRALIA’S NANOTECHNOLOGY WORK HEALTH & SAFETY PROGRAM 61

62 Nanotechnology WHS Program Managed by the Safe Work Australia agency Supported by funding under National Enabling Technologies Strategy National groups –Nanotechnology Work Health & Safety Advisory Group –Nanotechnology Work Health & Safety Measurement Reference Group

63 Program Focus Areas Nanotechnologies & WHS regulatory framework Hazardous properties of manufactured nanomaterials Effectiveness of workplace controls Emissions and exposure measurement Information for nanotechnology organisations Participating in international initiatives & consistency with international approaches

64 Published Research Reports Plus Durability of carbon nanotubes and their potential to cause inflammation Nanoparticles from printer emissions in workplace environments Health effects of laser printer emissions measured as particles Human health hazard assessment and classification of carbon nanotubes

65 Other Nanotechnology WHS information On Safe Work Australia website - WHS assessment tool for handling engineered nanomaterials Guidance - Safe handling & use of carbon nanotubes (CSIRO 2012) Information sheets −Use of laser printers −Safe handling of carbon nanotubes −Measuring and assessing emissions and exposures −Classification of carbon nanotubes as hazardous chemicals −Safety hazards of nanomaterials −Emissions of nanomaterials during machining processes Elsewhere, for example: WHS Regulators websites ACTU website OECD Working Party for Manufactured Nanomaterials & ISO documents

66 Research, Regulation, Guidance & Training - For Carbon Nanotubes Understanding hazards –Reviews of nanomaterials health hazards & safety hazards (Toxikos) –Durability of carbon nanotubes and their potential to cause inflammation (CSIRO/IOM/Edinburgh University) Regulation –Health hazard assessment & recommended classification (NICNAS) Measurement of carbon nanotubes emissions/exposures –Detection in the workplace (CSIRO) –Determining/validating suitable techniques (QUT/WHSQ) –Potential emissions from solid articles from machining (CSIRO) Guidance & training materials –Safe handling & use of carbon nanotubes (CSIRO) –Nanotechnology WHS training course (draft, RMIT University)

67 Summary Obligations under Work Health and Safety legislation need to be met for nanomaterials and nanotechnologies Safety by design – Effective design of workplace engineering controls is critical Limited information on hazards of nanomaterials Conventional controls can be used to minimise exposure –take precautionary approach in choosing controls

68 Further Information