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Guidance on handling and use of nanomaterials
Miriam Baron
Federal Institute for Occupational Safety and
Health, Germany
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Overview

• Questionaire
• Guidance for Handling and Use of Nanomaterials at
  the Workplace
• Threshold limit values
• Nanodialog

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BAuA-questionaire 2006

• 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

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BAuA-questionaire 2006 Situation in Germany

• 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

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Questionary Activities (out of 70 products)

• 96 working situations
• 37 mixing and dispersing
• 31 filling and baging
• 17 loading and decanting
• 7 drying
• 4 milling
• Multiple responses possible

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Questionary Knowledge gaps (out of 70 products)

• 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

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Questionary Protection measures (out of 70
products)

• Protection Measures
• Engineering controls 54
• Ventilation 63
• Personal protective equipment 55 (respiratory
  protection)
• Multiple responses possible

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Questionary Protection measures Engineering
Controls

• Engineering controls (54 cases)
• Wet processing 37
• Closed system 27
• Automatic processing 13
• Multiple responses possible

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Questionary Protection measures - ventilation

• Ventilation (63 cases)
• Open ventilation 29
• Semi-open ventilation 21
• Automatic ventilation 18
• Closed ventilation 13
• Natural ventilation 9
• Multiple responses possible

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Questionary Protection measures personal
protective equipment

• 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

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Guidance for Handling and Use of Nanomaterials at
the Workplace

• 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)

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Contents
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
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General occupational health and safety rules
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
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Information gathering
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)
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Information gathering

• 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.

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Determination of protection measures

• STOP-Principle
• Substitution options
• Technical measures
• Organizational measures
• Personal protection measures

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Determination of protection measures

• 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

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Substitution options

• 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

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Technical protection measures

• 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

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Organizational protection measures I

• 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

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Organizational protection measures II

• 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

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Personal protection measures

• 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

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Personal protection measures (respiratory
protection)

• 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

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Personal protection measures (dermal protection)

• 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

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Further protection measures

• 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

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Flowchart Hazard assessment for Nanoparticles at
the Workplace (respiratory route)
No
Yes
Yes
Yes
Activities in laboratories or small volumes?
Risks due to explosions, reactive or
catalyticallyactive nanoparticles?
Does the activity involve dust formation?
Is there a low hazard?
No
Yes
No
No
Can dispersion, solid granules,compounds be
used?
Open systems?
Process avoids dust and aerosol formation
because of closed system?
Sucking up with integrated or highly efficient
equipment?
No
No
No
Yes
Yes
Yes
Yes
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Hazard assessment

• With respect to
• Substance related hazards including
• Properties
• Physical state
• Processing options
• Further hazards (e.g. electrical or mechanical)

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Hazardous Substances Ordinance - Principles

• 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.

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European Community/German Legislation

• 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)

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Data gaps (TRGS 400/TRGS 526)
Minimal hazard properties in case of
uncertainties R20/21/22 Harmful by inhalation,
in contact with skin and if swallowed. R38 Irr
itating to skin R43 May cause sensitization by
skin contact R68 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
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Information down the supply chain
Technical Data Sheet for Application Material
Safety Data Sheet Accompanying Letter
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Material safety data sheet (MSDS)

• 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

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Existing threshold limit values (TLVs)

• 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/m3e. 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
  four
• classes 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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Nano dialog

• Stakeholder dialogNGO, 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

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Nano commission Five basic Principles for a
Responsible Use of Nanomaterials

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

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Thanks to

• 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)

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Further questions
Miriam Baron Federal 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_at_baua.bund.de www
http//www.baua.de
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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/Default2cmdget_dwnlddocnr121
  306fileLeitfadenNano5Fengl5FFINAL2Epdf.htm
• Nano-Dialog
• http//www.bundesumweltministerium.de/english/nano
  technology/nanodialog/doc/40549.php
• Other
• http//www.baua.de/en/Topics-from-A-to-Z/Hazardous
  -Substances/Nanotechnology/Nanotechnology.html?__n
  nntrue__nnntrue
• http//www.ilo.org/public/english/protection/safew
  ork/ctrl_banding/toolkit/other_toolkits/nanotool_s
  ynopsis.pdf
• http//www.bmu.de/gesundheit_und_umwelt/nanotechno
  logie/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_VCIIntern
  et/122301Guidance20SDS20for20Nanomaterials20_0
  620March202008DokNr122301p101.pdf
• http//www.bmbf.de/en/nanotechnologie.php