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

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

Nanotechnology Work Health & Safety

Engineers Australia SeminarCanberra, 21 March 2013

Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

1

Page 2: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Page 3: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Page 4: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

INTRODUCTION TO NANOTECHNOLOGY

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Page 5: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

Nanotechnology - Definitionsnanotechnology (ISO TS 80004-1:2010 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

Page 6: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

About Nanomaterialsnanomaterial 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

Page 7: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

Particle Size Comparison

10

Animal, plant or fungi membrane

cells

Page 8: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

Different Types of Nanomaterials

Naturally Occurring

Human Origin (Incidental)

Human Origin (Engineered/

Manufactured)

Forest fires Cooking smoke Metals

Sea spray Diesel exhaust Quantum dots

Mineral composites Welding fumes Nanotubes & Nanowires

Volcanic ash Industrial effluents Metal oxides

Viruses Sandblasting Fullerenes

NanotechnologyAdapted from: Lippy and Kulinowski

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Page 9: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

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Page 10: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

Red Gold

Nano Gold = RedLoses conductivity at ~ 1-3 nmBecomes magnetic ~ 3 nmExplosive and catalytic

Gold (~ 10 nm)

Bulk Gold (Au) = YellowConductiveNonmagneticChemically inert

16 nm gold

National Measurement Institute,(NMI) Australia

Source: Lippy and Kulinowski

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Page 11: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

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Page 12: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

Nano-Enabled Glasses• Glasses

– Self cleaning glass– Low reflective glass– Switchable glass

Source: AccessNano (adapted)

self cleaning normal

glassglass

14

OptiViewTM Low reflective glassMade by Pilkington

Page 13: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

Detecting Cancer Cells

Breast Cancer Res Treat (2010) 120:547–555

with nanoshells

without nanoshells

normal HER2- 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

Page 14: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

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Page 15: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

WORK HEALTH AND SAFETY LEGISLATION

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Page 16: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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)

Page 17: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 18: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Page 19: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 20: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

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

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Duties of DesignersModel 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

Page 22: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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.

Page 23: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

APPLYING THE WORK HEALTH AND SAFETY LEGISLATION TO NANOMATERIALS

23

Page 24: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Page 25: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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Taking a Precautionary ApproachThere 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

Page 26: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 27: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

NANOMATERIAL HAZARDS

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Page 28: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

Health impacts of emissions containing incidental nanoparticles

Human Origin (Incidental) Health Impacts

Cooking smokePneumonia; chronic respiratory disease; lung cancer

Diesel exhaustCancer; respiratory diseaseIARC classified diesel engine exhaust as carcinogenic to humans (2012)

Welding fumes Metal fume fever; infertility; benign pneumoconiosis

Sandblasting Silicosis

Adapted from: Drs Lippy and Kulinowski

28

Considerable knowledge on health impacts of fine & ultrafine particulate air pollution

Page 29: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 30: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

Exposure Pathway Model

ProcessWork

surfaces

SkinIngestion

Inhalation

Skin absorption

Air

38

Source: Drs Lippy and Kulinowski, from Mulhausen and Damiano

Page 31: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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: http://upload.wikimedia.org/wikipedia/commons/3/36/Respiratory_Tract.png

Source: Drs Lippy and Kulinowski

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Page 32: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Toxicology Consultants Source:

Page 33: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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 GranulomaCancer (mesothelioma)

Toxicology Consultants Source:

Page 34: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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 NanotubeCourtesy of R. Mercer, NIOSH

Page 35: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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. 2010 Nov;118(1):

B.Gulson, M.McCall et al

Skin cannot be ruled out as a potential route of exposure

35

Page 36: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 37: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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 hazardousCarcinogenicity: Category 2Specific target organ toxicity - repeated exposure: Category 2

Not classified as hazardous

Acute toxicity: Oral, DermalSerious eye irritationSkin irritationSkin sensitisationSpecific target organ toxicity - single exposure

Cannot be classified

Acute toxicity: InhalationRespiratory sensitisation Germ cell mutagenicity Reproductive toxicity

Page 38: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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)

Page 39: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Page 40: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Page 41: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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)

Page 42: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

Evaluation of potential safety hazards

• Minimum explosive concentration (MEC) is significantly higher (30-70g/m3) 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)

Page 43: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

ELIMINATING OR MINIMISING EXPOSURE TO NANOMATERIALS

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Page 44: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 45: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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 workingin fume cabinet withengineered nanomaterials (CSIRO, 2009)

Page 46: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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Level 2 – Substitution & ModificationSubstitution more likely than elimination• Issue – maintaining product properties

C. Sayes et al. (2004) Nano Letters 4(10):1881-87

Page 47: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Page 48: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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Effectiveness of Engineering Controls

Number of CNTs/cm3

Before process enclosure

After process enclosure

Personal 193.6 0.018

Area 172.9 0.05

Process enclosureBlending with carbon nanotubes for composites.

(Han et al, Inhalation Toxicology, 2008)

Process 2 - C

0.00E+00

1.00E+04

2.00E+04

3.00E+04

4.00E+04

5.00E+04

6.00E+04

7.00E+04

11:0

2

11:1

6

11:3

1

11:4

5

12:0

0

12:1

4

12:2

8

12:4

3

12:5

7

13:1

2

Time

Par

ticl

e N

um

ber

Co

nce

ntr

atio

n (

p cm

-3)

CPC3781 background CPC3781 at source

release artificial smoke

extrusion machine started - polyurethane additive only clay

added to hopper

opened extruder plate

local extractionventilationturned on

extraction turned off

extraction turned back on

extrusion stopped

LEV EffectivenessFrom McGarry et al (QUT/WHSQ 2012)

Page 49: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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RMIT University©2010 NanoSafe Australia 49

Nanoparticle FiltrationFibrous 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) 150-300 nm

(EU Nanosafe2, Jan 2008)

Page 50: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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)

Page 51: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Page 52: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

Page 53: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

MEASURING & ASSESSING EXPOSURE TO NANOMATERIALS

53

Page 54: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Particle Diameter / nm

10 100d

N/d

log

dP /

cm-3

0.0

2.0e+4

4.0e+4

6.0e+4

8.0e+4

1.0e+5

1.2e+5

after 16minafter 32minafter 44minafter 60minafter 76minafter 92min

Size distributions of Pt particles after release in a clean exposure chamber. NANOTRANSPORT (2008): The Behaviour of Aerosols Released to Ambient Airfrom Nanoparticle Manufacturing

Page 55: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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)

Page 56: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 57: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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Exposure Standards

Type of Standard/Limit

Substance Size of material Exposure Standard/Limit8 or 10 hour TWA, mg/m33

Australian WES Graphite (all forms except fibres)

Respirable 3 (respirable)

Australian WES Carbon black Nanomaterial 3 (inhalable)

US NIOSHProposed REL

Carbon nanofibres, including CNTs

Nanomaterial 0.007

Japan AISTProposed EL

Fullerenes Nanomaterial 0.39

Australian WES Crystalline silica Respirable 0.1 (respirable)

Australian WES Amorphous silica Inhalable 10 (inhalable)

Australian WES Fumed silica Nanomaterial 2 (respirable)

US NIOSH REL TiO2 Nanomaterial 0.3

US NIOSH REL TiO2 Fine size fraction 2.4

Australian WES TiO2 Inhalable 10 (inhalable)

Page 58: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

NANOWASTE

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Page 59: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

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http://cohesion.rice.edu/centersandinst/icon/emplibrary/Mustafa_Nanomaterials%20Workshop-Houston-Texas(FINAL).ppt

Page 60: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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

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Page 61: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

SAFE WORK AUSTRALIA’S NANOTECHNOLOGY WORK HEALTH &

SAFETY PROGRAM

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Page 62: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 63: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 64: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 65: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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Other Nanotechnology WHS informationOn Safe Work Australia website - www.safeworkaustralia.gov.au• 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

Page 66: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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)

Page 67: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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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

Page 68: Nanotechnology Work Health & Safety Engineers Australia Seminar Canberra, 21 March 2013 Presenters: Ian Ireland (Comcare) & Howard Morris (Safe Work Australia)

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Further Information

www.safeworkaustralia.gov.au