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Guidance on handling and use of nanomaterials Miriam Baron Federal Institute for Occupational Safety and Health, Germany Overview • Questionaire • Guidance for Handling and Use of Nanomaterials at the Workplace • Threshold limit values 23.04.2009 • Nanodialog 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 23.04.2009 • Small and medium enterprises 3 • Research companies 4.6/Baron 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) 23.04.2009 • 56 % produce/use more than one nanomaterial 4 • 71 % less than 10 exposed employees • Reported products: 70 4.6/Baron Questionary: Activities (out of 70 products) 96 working situations: • 37 mixing and dispersing • 31 filling and baging • 17 loading and decanting • 7 drying 23.04.2009 • 4 milling Multiple responses possible 5 4.6/Baron 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 23.04.2009 No particle-specific health complaints among the workers were reported Multiple responses possible 6 4.6/Baron Questionary: Protection measures (out of 70 products) Protection Measures 54 • Ventilation 63 • Personal protective equipment (respiratory protection) 55 23.04.2009 • Engineering controls Multiple responses possible 7 4.6/Baron Questionary: Protection measures – Engineering Controls 23.04.2009 Engineering controls (54 cases) 8 • Wet processing 37 • Closed system 27 • Automatic processing 13 Multiple responses possible 4.6/Baron Questionary: Protection measures ventilation 23.04.2009 Ventilation (63 cases) 9 • Open ventilation 29 • Semi-open ventilation 21 • Automatic ventilation 18 • Closed ventilation 13 • Natural ventilation 9 Multiple responses possible 4.6/Baron 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 23.04.2009 specific respirators (FFP1 to FFP3) 10 Multiple responses possible 4.6/Baron 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 23.04.2009 • To be amended by industry sector specific Guidance (under progress: for laboratories) 11 4.6/Baron 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 23.04.2009 Annex 12 4.6/Baron Flowchart on Hazard Assessment for Nanomaterials at the Workplace General occupational health and safety rules Duties according to the Hazardous Substances Ordinance: Information gathering 2. Hazard assessment 3. Determination of protection measures 4. Review of effectiveness of measures 5. Documentation 23.04.2009 1. 13 4.6/Baron Information gathering • Used product (properties, volume, type and form of use). 23.04.2009 • Activity (possible intake: by inhalation, dermal or oral). For oxidizable materials, also fire and explosion risks must be included 14 • Substitution options (including any use of processes or preparations of the substance that result in lower hazard) 4.6/Baron Information gathering • Effectiveness of protection measures already in place • Implemented activities in preventive occupational medicine 23.04.2009 • In case of data gaps, this lack of information must be adequately taken into account when determining protection measures. 15 4.6/Baron Determination of protection measures STOP-Principle 1. Substitution options 2. Technical measures 3. Organizational measures 23.04.2009 4. Personal protection measures 16 4.6/Baron 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 23.04.2009 • Available measurement data 17 • To be used for assessment at a later stage 4.6/Baron Substitution options • Replacing health-endangering substances or technical processes by less ones • Binding powder nanomaterials in liquid or solid media 23.04.2009 • Using dispersions, pastes or compounds instead of powder substances wherever technically feasible and economically acceptable 18 4.6/Baron 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 23.04.2009 • No recirculation without exhaust air purification 19 4.6/Baron 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 23.04.2009 • Keep the number of potentially exposed workers as small as possible (e.g. by time arrangements) 20 • Deny unauthorized persons access to the relevant work areas 4.6/Baron 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 23.04.2009 • Wiping up with a moist cloth 21 • No blowing for removal 4.6/Baron 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 23.04.2009 • Respiratory protection equipment 22 4.6/Baron 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) 23.04.2009 • “Total number penetration efficiency" P3 filters penetration less than 0.026% (particle count) P2 filters penetration of 0.2% (particle count) 23 • Effectiveness must be reviewed 4.6/Baron 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 23.04.2009 • Additional protection of other areas of skin by 24 • Protective suits • Aprons • Boots 4.6/Baron 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 23.04.2009 • Conventional measures resulting from the hazard assessment 25 4.6/Baron Flowchart: Hazard assessment for Nanoparticles at the Workplace (respiratory route) Specific hazard assessment No Hazard No Yes Risks due to explosions, reactive or catalytically active nanoparticles? Work in extractor, requirements according to TRGS 526 General occupational Hygiene measures Yes Does the activity involve dust formation? No Yes Activities in laboratories or small volumes? Is there a low hazard? Yes No No Open systems? No 23.04.2009 Yes 26 Organizational measures Personal protective equipment 4.6/Baron Sucking up with integrated or highly efficient equipment? Yes Efficiency testing in regular intervals, instruction, demarcation of work area Process avoids dust and aerosol formation because of closed system? No Yes Efficiency testing in regular intervals, instruction No Can dispersion, solid granules, compounds be used? Yes Examine substitutions options Hazard assessment With respect to: • Substance related hazards including • Properties • Physical state • Processing options 23.04.2009 • Further hazards (e.g. electrical or mechanical) 27 4.6/Baron Hazardous Substances Ordinance - Principles Risk assessment by the employer before starting activities • Eliminating Risks • Minimize Risks In case of uncertainty: 23.04.2009 • 28 Precautionary principle „The need for control measures increases with both the level of possible harm and the degree of uncertainty.“ 4.6/Baron 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 23.04.2009 Handling: 29 Hazardous Substances Ordinance (based on European directive 98/24/EC) 4.6/Baron Data gaps (TRGS 400/TRGS 526) Minimal hazard properties in case of uncertainties: R20/21/22 R38 R43 R68 Harmful by inhalation, in contact with skin and if swallowed. Irritating to skin May cause sensitization by skin contact Possible risk of irreversible effects 23.04.2009 Unknown new substances in research: Toxic by inhalation, in contact with skin and if swallowed 30 Additionally: corrosive, (spontaneous) flammable, explosive 4.6/Baron Information down the supply chain Technical Data Sheet for Application Material Safety Data Sheet 23.04.2009 Accompanying Letter 31 4.6/Baron 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” 23.04.2009 • Standard test methods are used to derive risks 32 • Measures are not justified with risks 4.6/Baron Existing threshold limit values (TLV’s) TLVs for poorly soluble dusts/fibers with specific toxicity •Quartz: •Silver (metal): •Asbestos: 0.075 0.01 0.01 – 0.3 – 0.1 –2 mg/m³ mg/m³ 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 23.04.2009 Covering also the nano sized fraction 33 • Legally binding TLVs specifically for nanomaterials are very rare (Amorphous silica: 2 to 6 mg/m³) 4.6/Baron Approaches for setting a TLV for nanomaterials (1) Draft exposure limits from NIOSH (USA, 2005) for titanium dioxide: 23.04.2009 • • • 34 • • 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 4.6/Baron 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: CMAR nanomaterials: Soluble nanomaterials: 23.04.2009 • • • 35 4.6/Baron 0.066 of TLV (NIOSH relation of 15) 0.1 of TLV 0.5 of TLV Nano dialog • 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 23.04.2009 • First period 2006 – 2008, will be elongated to 2010 36 • First Report just released 4.6/Baron 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 23.04.2009 4. Established Risk management 37 5. Responsibility down the supply chain 4.6/Baron 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) 23.04.2009 • Dr. Eva Lechtenberg-Auffahrt (Occupational safety) 38 4.6/Baron Further questions: Miriam Baron Federal Institute for Occupational Safety and Health (BAuA) Unit 4.6 “Hazardous Substances Management” Friedrich-Henkel-Weg 1-25 D-44149 Dortmund Germany 23.04.2009 mail-to: [email protected] 39 www: 4.6/Baron http://www.baua.de 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/HazardousSubstances/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-SubstancesOrdinance.pdf 23.04.2009 http://www.vci.de/template_downloads/tmp_VCIInternet/122301Guidance%20SDS%20for%20Nanomaterials%20 _06%20March%202008~DokNr~122301~p~101.pdf 40 http://www.bmbf.de/en/nanotechnologie.php 4.6/Baron