IVAM research and consultancy on sustainability1 AWARE code Adequate Warning and Air Requirement a tool for substitution and workplace improvement Hildo Krop IVAM Amsterdam Pieter van Broekhuizen IVAM Amsterdam

IVAM research and consultancy on sustainability2 AWARE technical working group Ministry of Social Affairs FME-CMW (Association metal and electronics industry) FOSAG / SVMB (Association painters and paint maintenance) Brenntag (Cleaning agents manufacturer) Trade Unions IVAM and QA+

IVAM research and consultancy on sustainability3 This presentation Part I Background and AWARE 1 derivation Comparison AWARE 1 vs OAR/MAL 1 Part II AWARE 1 code for spraying and AWARE 2 code Part III AWARE code results and comparisons

IVAM research and consultancy on sustainability4 Background AWARE AWARE 1 derivation and Comparison AWARE 1 versus OAR/MAL 1 Part I

IVAM research and consultancy on sustainability5 Background Tool to support substitution Integrated approach to reduce inhalatory exposure to hazardous substances, especially OPS prevention Substitution obligation in several industrial sectors Generic approach for solvent borne products

IVAM research and consultancy on sustainability6 Starting-point considerations Experiences in Norway and Denmark with OAR and MAL Feasibility studies in NL of the OAR/MAL codes In line with information requirements in the product chain Transparent system Lacking info leads to the use of default value(s) Focus on substitution, not on protective measures Introduction of a physical/chemical approach to derive AWARE Critical evaluation and validation of the developed method  Users Not only brush but also spray application

IVAM research and consultancy on sustainability7 Resulting AWARE code Based on the Ready-For-Use product Potential risk indicator with two digits: AWARE 1 - AWARE 2 for example: AWARE 1 (850) = the volume of fresh air (m 3 ) required to dilute the air in the working space after the use of 1 L of the product to concentrations below the level of the combined OELs AWARE 2 (IV) = Indicator for identified hazards of all components of the product 850 – IV

IVAM research and consultancy on sustainability8 Derivation of the AWARE 1 Margin of Safety Kinetic approach: Static approach: Assumptions 1.No toxic interaction of components (additivity of effects) 2.Distinction between exposure to volatile and non-volatile substances 3.Volatile toxic interaction  non-volatile toxic interaction

IVAM research and consultancy on sustainability9 Evaporation models Kinetic approach Complex additivity of fluxes, resistances, wind speed, paint film formation etc. Many unknown parameters Too complex for “simple” AWARE derivation Static Approach Easier applicable with some assumptions AWARE 1 based on original product composition (t = 0) Ideal behaviour of liquids supposed: Follow Raoult’s law Definition volatile and non-volatile conform VOC Directive

IVAM research and consultancy on sustainability10 AWARE 1 versus OAR and MAL 1 Differences between AWARE and OAR/MAL f is dimensionless and defined as ~ P eq / P i eq,max is limited by a maximum based on V of 1 L for P i eq > Pa  f =1 More realistic (Gliding scale) evaporation factor f AWARE 1 <(<) OAR or MAL 1 AWARE 1 relatively more favourable for liquids with low P eq AWARE 1 is air requirement just above the liquid film

IVAM research and consultancy on sustainability11 AWARE 1 vs OAR/MAL 1 Equilibrium vapor pressure Pa (20 °C) Evaporation factor f OAR/MAL 1 approach Evaporation factor f AWARE-code  < p v  – < p v  – < p v  – < p v  – 0.89 p v > Substance (All d = 1) P eq (Pa) OEL (mg/m3) % (m) in product OAR (m 3 /L) AWARE (m 3 /L) Toluene Hypothetic Acetone

IVAM research and consultancy on sustainability12 Other aspects in the AWARE 1 1.Adaptation for dissolved gaseous substances (e.g. formaldehyde) Based on Henry’s Law Henry values gaseous substances available in database Applicable for water-based products In practice only a few substances involved (~ well soluble in water) 2.OEL selected according to hierarchy priority list 3.In case no established OEL value, default based on R-phrase 4.Monomer contribution taken into account Default monomer type established in case of lacking info Default monomer concentration established in case of lacking info More info available  less use of defaults 5.OELs and vapour pressures established for mineral spirit fractions 6.In case of lack of full product information: MSDS-info for composition and mass range used

PART II AWARE 1 code for spraying and AWARE 2 code

IVAM research and consultancy on sustainability14 AWARE 1 code for spraying (I) Evaporation rate droplets of volatile substances much higher than brush application surface area A of droplets much larger P eq higher due to Kelvin effect (Radius droplets decrease (A  ) but rate  due to P eq  ) Toxicological effects volatile fraction differs from non-volatile fraction Contribution of respirable fraction of non-volatile substances Depends on gun spraying efficiency, S E (default 50%) 10% of the non-deposited fraction available for inhalation = {0.1*(1-S E )}

IVAM research and consultancy on sustainability15 AWARE 1 code for spraying (II) Contribution volatile fraction to AWARE 1 Fraction deposited on subject behaves as in brush application Fraction not deposited (airborne fraction) is evaporated instantaneously Fraction deposited depends on efficiency of spraying gun, S E (default 50%) Final value for the AWARE 1 code for spraying application is determined by: the largest value of the volatile or the non-volatile

IVAM research and consultancy on sustainability16 AWARE 2 code numbers 1.Different toxic effects not included in the AWARE 1 (corrosivity, allergenicity, carcinogenicity etc) 2.R-phrase according to Dangerous Preparation Directive 3.AWARE 2 ranked in 5 classes (I – V) according to toxicity 4.Ranking table derived from other classification systems systems (IT-score, GWF, SOMS, ILO, MAL-2) 2.R67 not included in the AWARE 2

IVAM research and consultancy on sustainability17 Comparison AWARE 2 and MAL 2 AWARE 2 5 classes – MAL 2 7 classes MAL: adds all (toxic) substances in the same class to determine MAL 2 AWARE: the most toxic component determines the AWARE 2 (slight) differences in limit weight percent

IVAM research and consultancy on sustainability18 PART III AWARE code calculations and comparisons

IVAM research and consultancy on sustainability19 AWARE – calculation Metalcoating paint

IVAM research and consultancy on sustainability20 AWARE calculation Furniture Lacquers, brush/roller application II III II IV

IVAM research and consultancy on sustainability21 AWARE calculations High P eq, very low OEL and below VIB limit

IVAM research and consultancy on sustainability22 AWARE calculations

IVAM research and consultancy on sustainability23 AWARE calculations

IVAM research and consultancy on sustainability24 Conclusions Improved theoretical basis for the evaporation factor Comprehensible transparent system Tool can be used by users only (Info from MSDS and PIS) Triggers chain communication Triggers substitution by formulators and users Distinguishes between different and within product classes Useful for spray application Contrary to OAR/MAL banding of f and value not necessary

IVAM research and consultancy on sustainability25 Limitations No variation of the concentration of the vapors in time considered No inclusion of work space size and dilution of vapors Default concentrations of monomers in binders (old data) Discrepancy full vs MSDS when formulation contains a highly volatile substance with very low OEL below VIB limit

IVAM research and consultancy on sustainability26 Future activities Pilot project in metal industry, shoe repair, furniture industry Validating codes with exposure measurements Further improve the tool (user friendliness, scientific article, database) Assistance to the users of the tool Creating support to be used as an EU substitution tool

IVAM research and consultancy on sustainability27