23.04.2009

Guidance on handling and use of nanomaterials

Miriam Baron

Federal Institute for Occupational Safety and Health, Germany

23.04.

2009

Overview

• Questionaire

• Guidance for Handling and Use of Nanomaterials at

the Workplace

• Threshold limit values

• Nanodialog

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• Initiated by the stakeholder dialog event on

engineered nanoparticles (october 2005)

• Cooperation with:• German Chemical Industry Association (VCI)

• Federation of German Industries (BDI)

• 217 companies participated:• Industry

• Small and medium enterprises

• Research companies

BAuA-questionaire 2006

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• Participation according to the criterion: use of nanomaterials above 10 kg/yr

• 45 companies participated:• 51 % use above 100 kg/yr

• Thereof 11 % above 100 t/yr

• Thereof 7 % above 1000 t/yr (e.g. carbon black, silicic acid)

• 56 % produce/use more than one nanomaterial

• 71 % less than 10 exposed employees

• Reported products: 70

BAuA-questionaire 2006: Situation in Germany

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96 working situations:

• 37 mixing and dispersing

• 31 filling and baging

• 17 loading and decanting

• 7 drying

• 4 milling

Multiple responses possible

Questionary: Activities (out of 70 products)

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• No knowledge on particle size and number

59

• No measurement (unknown exposure)

31

• No knowledge about potential health effects

28

No particle-specific health complaints among the

workers were reported

Multiple responses possible

Questionary: Knowledge gaps (out of 70 products)

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Protection Measures

• Engineering controls 54

• Ventilation 63

• Personal protective equipment 55

(respiratory protection)

Multiple responses possible

Questionary: Protection measures (out of 70 products)

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Engineering controls (54 cases)

• Wet processing

37

• Closed system

27

• Automatic processing

13

Multiple responses possible

Questionary: Protection measures – Engineering Controls

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Ventilation (63 cases)

• Open ventilation

29

• Semi-open ventilation

21

• Automatic ventilation

18

• Closed ventilation

13

• Natural ventilation

9

Multiple responses possible

Questionary: Protection measures - ventilation

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• For 80 % of the activities: usage of respiratory

protection (additionally to engineering controls and

ventilation)

• Wide spectrum, ranging from general masks to

specific respirators (FFP1 to FFP3)

Multiple responses possible

Questionary: Protection measures – personal protective equipment

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• Cooperation with the German Chemical Industry

Association (VCI)

• Published 2007

• To be updated this year

• To be amended by industry sector specific

Guidance (under progress: for laboratories)

Guidance for Handling and Use of Nanomaterials at the Workplace

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1 Introduction

2 General occupational health and safety rules

3 Recommendations for workers' protection in the

handling and use of nanomaterials

4 Current situation and development of measuring

methods for nanoparticles

Annex Flowchart on Hazard Assessment for

Nanomaterials at the Workplace

Contents

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Duties according to the Hazardous Substances

Ordinance:

1. Information gathering

2. Hazard assessment

3. Determination of protection measures

4. Review of effectiveness of measures

5. Documentation

General occupational health and safety rules

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• Used product

(properties, volume, type and form of use).

• Activity

(possible intake: by inhalation, dermal or oral).

For oxidizable materials, also fire and explosion

risks must be included

• Substitution options (including any use of processes

or preparations of the substance that result in lower

hazard)

Information gathering

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• Effectiveness of protection measures already in

place

• Implemented activities in preventive occupational

medicine

• In case of data gaps, this lack of information must

be adequately taken into account when determining

protection measures.

Information gathering

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STOP-Principle

1. Substitution options

2. Technical measures

3. Organizational measures

4. Personal protection measures

Determination of protection measures

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• Review of measure effectiveness in place

• Comparative inspection with measurement

• Documentation

• Firstly hazard assessment including:

• Substances used

• Working conditions

• Protection measures taken

• Available measurement data

• To be used for assessment at a later stage

Determination of protection measures

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• Replacing health-endangering substances or

technical processes by less ones

• Binding powder nanomaterials in liquid or solid

media

• Using dispersions, pastes or compounds instead of

powder substances wherever technically feasible

and economically acceptable

Substitution options

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Contained installations, wherever possible

• Otherwise avoid the formation of dusts or aerosols

• Extract possibly forming dusts or aerosols directly at

their source (e.g. in filling and emptying processes)

• Ensure regular maintenance and function testing of

extraction facilities

• No recirculation without exhaust air purification

Technical protection measures

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• Instructions to the workers, including

• Specific physical properties of free nanoparticles

• Need for special measures

• Potential long-term effects of dusts

• Relevant information in the operating instructions

• Limitation of exposed persons

• Keep the number of potentially exposed workers as small as

possible (e.g. by time arrangements)

• Deny unauthorized persons access to the relevant work

areas

Organizational protection measures I

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• Ensure clean work wear

• Work wear must be cleaned by the employer

• Work wear and private clothing must be stored separately

• Ensure the regular cleaning of workplaces

• Removing of deposits or spilled substances by

• Suction device

• Wiping up with a moist cloth

• No blowing for removal

Organizational protection measures II

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• Only where technical protection measures are not

sufficient or cannot be put into place

• Depending on substance properties

• Protective gloves

• Protection goggles with side protection

• Protective clothing

• Respiratory protection equipment

Personal protection measures

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• Efficacy of filters increases with decreasing particle

size in the size range between 2-200 nm

• Measuring data from BGIA

(on sodium chloride particles from 14 to 100 nm)

• “Total number penetration efficiency"

P3 filters penetration less than 0.026% (particle count)

P2 filters penetration of 0.2% (particle count)

• Effectiveness must be reviewed

Personal protection measures (respiratory protection)

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• Selection of gloves:

• Material must be suitable

• Material must fulfill requirements for maximum wearing time

under practical conditions

• Permeation time is important relevant criterion

• Additional protection of other areas of skin by• Protective suits• Aprons• Boots

Personal protection measures (dermal protection)

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• Depending on the properties of specific nanomaterials

• Anti-explosion measures in the handling of oxidizable

nanomaterials

• Specific protection measures in the handling of

reactive or catalytic nanomaterials

• Conventional measures resulting from the hazard

assessment

Further protection measures

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Specific hazard assessment

Risks due to explosions, reactive or catalyticallyactive nanoparticles?

Does the activity involve dust formation?

No Hazard

Is there a low hazard?

General occupationalHygiene measures

Activities in laboratories or small volumes?

Work in extractor, requirements

according to TRGS 526

Can dispersion, solid granules,

compounds be used?

Examine substitutionsoptions

Process avoids dust and aerosol formation

because of closed system?

Efficiency testing in regular intervals, instruction

Efficiency testing in regular intervals, instruction,

demarcation of work area

Sucking up with integrated or

highly efficient equipment?Open systems?

Organizational measuresPersonal protective

equipment

Flowchart: Hazard assessment for Nanoparticles at the Workplace (respiratory route)

Yes No Yes Yes

YesYesYesYes

No Yes No

No

NoNoNo

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With respect to:

• Substance related hazards including

• Properties

• Physical state

• Processing options

• Further hazards (e.g. electrical or mechanical)

Hazard assessment

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Risk assessment by the employer before starting activities

• Eliminating Risks

• Minimize Risks

In case of uncertainty:

• Precautionary principle

„The need for control measures increases with both the

level of possible harm and the degree of uncertainty.“

Hazardous Substances Ordinance - Principles

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Placing on the market:

REACH (European regulation 2006/1907/EC)

• Applicable for nanomaterials

• With reference to the substance

• (optionally) consideration of the nanoform in the Chemical Safety

Report (CSR)

• if necessary additional proofs concerning the special nanoform

Handling:

Hazardous Substances Ordinance

(based on European directive 98/24/EC)

European Community/German Legislation

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Minimal hazard properties in case of uncertainties:R20/21/22 Harmful by inhalation,

in contact with skin and if swallowed.R38 Irritating to skinR43 May cause sensitization by skin contactR68 Possible risk of irreversible effects

Unknown new substances in research:Toxic by inhalation, in contact with skin and if swallowed

Additionally: corrosive, (spontaneous) flammable,

explosive

Data gaps (TRGS 400/TRGS 526)

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Technical Data Sheet for Application

Material Safety Data Sheet

Accompanying Letter

Information down the supply chain

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• Information about substance properties and

occupational safety measures.

• Problem:

Handling of nano properties is not regulated

• Usual MSDS states:

“This substance has no dangerous properties”

• Standard test methods are used to derive risks

• Measures are not justified with risks

Material safety data sheet (MSDS)

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Existing threshold limit values (TLV’s)

TLVs for poorly soluble dusts/fibers with specific toxicity•Quartz: 0.075 – 0.3 mg/m³•Silver (metal): 0.01 – 0.1 mg/m³•Asbestos: 0.01 – 2 fibres/cm³

Generic TLVs: dusts with no specific toxicity• Inhalable dust/total dust : 4 - 15 mg/m³

• Respirable fraction (fine dust, lung) : 1.5 - 10 mg/m3

e. g. for titanium dioxide, graphite, iron oxide

Covering also the nano sized fraction• Legally binding TLVs specifically for nanomaterials are very rare

(Amorphous silica: 2 to 6 mg/m³)

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Approaches for setting a TLV for nanomaterials (1)

Draft exposure limits from NIOSH (USA, 2005) for titanium dioxide:

• Nanoscale titanium dioxide: 0.1 mg/m3

• Microscale titanium dioxide: 1.5 mg/m3

• Potency factor 15 between nanoparticles and microparticles based on long-term in vivo studies

• Reduction of risk of lung cancer below 1 in 1000

• Surface determines toxicity potential

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Approaches for setting a TLV for nanomaterials (2)

Benchmark levels (BL) from BSI (UK, 2007) for fourclasses of nanomaterials

Nano-BL• Fibrous nanomaterials (high aspect ratio): 0.01 fibres/cm3

Nano-BL in relation to established TLVs• Insoluble nanomaterials: 0.066 of TLV (NIOSH relation of

15)• CMAR nanomaterials: 0.1 of TLV

• Soluble nanomaterials: 0.5 of TLV

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• Stakeholder dialog:

NGO, Researcher, Industry, Other involved persons

• Leaded by the Nano commission

(temporary project group)

• Three Working parties on• Chances for environment and health• Risks and safety research• Principles for a responsible use of nanomaterials

• First period 2006 – 2008, will be elongated to 2010

• First Report just released

Nano dialog

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1. Defined Responsibility and management disclosed

(Good Governance)

2. Transparency regarding nanotechnology relevant

Information, Data and Processes

3. Willingness to the dialogue with Interest groups

4. Established Risk management

5. Responsibility down the supply chain

Nano commission: Five basic Principles for a Responsible Use of Nanomaterials

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My co-workers at BAuA

• Dr Torsten Wolf (Hazardous substances management)

• Dr Rolf Packroff (Hazardous and biological substances)

• Dr Bruno Orthen (Toxicology)

• Judith kleine Balderhaar (Database research)

• Sabine Plitzko (Measurement)

• Dr. Eva Lechtenberg-Auffahrt (Occupational safety)

Thanks to

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Miriam BaronFederal Institute for Occupational Safety and Health (BAuA)Unit 4.6 “Hazardous Substances Management” Friedrich-Henkel-Weg 1-25D-44149 Dortmund

Germany

mail-to: baron.miriam@baua.bund.de

www: http://www.baua.de

Further questions:

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Useful links/sources

Questionaire:

http://www.baua.de/nn_49456/en/Topics-from-A-to-Z/Hazardous-Substances/Nanotechnology/pdf/survey.pdf

Guidance:

http://www.vci.de/Default2~cmd~get_dwnld~docnr~121306~file~LeitfadenNano%5Fengl%5FFINAL%2Epdf.htm

Nano-Dialog:

http://www.bundesumweltministerium.de/english/nanotechnology/nanodialog/doc/40549.php

Other:

http://www.baua.de/en/Topics-from-A-to-Z/Hazardous-Substances/Nanotechnology/Nanotechnology.html?__nnn=true&__nnn=true

http://www.ilo.org/public/english/protection/safework/ctrl_banding/toolkit/other_toolkits/nanotool_synopsis.pdf

http://www.bmu.de/gesundheit_und_umwelt/nanotechnologie/doc/37643.php

http://www.baua.de/nn_39406/en/Topics-from-A-to-Z/Hazardous-Substances/TRGS/pdf/Hazardous-Substances-Ordinance.pdf

http://www.vci.de/template_downloads/tmp_VCIInternet/122301Guidance%20SDS%20for%20Nanomaterials%20_06%20March%202008~DokNr~122301~p~101.pdf

http://www.bmbf.de/en/nanotechnologie.php