Technical lessons and improvements to the AWARE code Conference on Product Codes within REACH Gent, 4 and 5 October Pieter van Broekhuizen

Derivation AWARE Starting-point considerations Product related code for VOC content Risk based approach Substitution support Simple, transparent system Useable with data available in public domain - SDS / Technical data / open literature

Product VOC-composition Airborne VOC exposure concentration Translation from paint to workplace air mg VOC/l paint mg VOC/m 3 workspace air

Product composition airborne exposure concentration Determining factors: -Amount of VOC in product- Toxicity -Density of the liquid- Vapour pressure Translation:  Product = liquids + solids evaporation  Molar fractions / Raoults law / Henry’s law / definition questions / acceptable assumptions / transformations (mol/l to Pa) / evaporation dynamics / etc. etc.  Workspace volume approaches zero  For liquids with P i eq > the evaporation is instanteous

Risk approach: Margin of Safety Margin of Safety: AWARE 1 approach: Concentration Occupational Exposure Limit Exposure concentration Total airborne concentration volatiles at workplace Combined OELs volatiles Vapour pressure component i

Final AWARE 1 AWARE 1 = is defined as the amount of fresh air (m 3 ), required to ventilate 1 m 3 of the working space, to dilute the evaporated volatiles after applying 1 liter of solvent containing product, at a room temperature of 20  C and an atmospheric pressure of 10 5 Pa, emitted from the surface of the treated object, which may lead to exposure of the worker, without adversely effecting the health of the worker. or: volume of fresh air (m 3 ) required to dilute the air in the working space after use of 1 L of the product to a concentration below the level of the combined OEL Where: d= density of the product (kg dm -3 ) c i = mass percentage of the solvent ‘i’ in the product (% (m/m)) f i = evaporation factor of solvent ‘i’ (0 ≤ f i ≤ 1) = P i eq / P i eq = equilibrium vapour pressure of component i at room temperature (Pa) OEL i = Occupational Exposure Limit of solvent ‘i’ (mg (solvent) m -3 (air))

AWARE 2 code numbers AWARE 2 = Indicator for identified hazards of the product 1.Different toxic effects (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 (IT-score, GWF, SOMS, ILO, MAL-2) 5.R67 not included in the AWARE 2

AWARE 2 coding

AWARE code  Based on the Ready-For-Use product  Potential risk indicator with two digits: AWARE 1 - AWARE 2

What developments in AWARE since 2006 ? 1.Fine tuning definition AWARE  AWARE restricted to manual application. For spraying application AWARE 1 development of SPARE (SPray Air Requirement)  AWARE definition at 20°C and 10 5 Pa For use at elevated temperature correction factor  For ventilation of 1 m 3 working space AWARE 1 used as input for calculation of workspace ventilation using a near field - far field approach (under development!)

What developments in AWARE since 2006 ? 1.Fine tuning definition AWARE  AWARE restricted to manual application. For spraying application AWARE 1 development of SPARE (SPray Air Requirement)  AWARE definition at 20°C and 10 5 Pa For use at elevated temperature correction factor  For ventilation of 1 m 3 working space AWARE 1 used as input for calculation of workspace ventilation using a near field - far field approach (under development!)

Vapour pressure multiplication factors for elevated temperature Derived by Clausius-Clapeyron equation using free enthalpy

What developments in AWARE since 2006 ? 1.Fine tuning definition AWARE  AWARE restricted to manual application. For spraying application AWARE 1 development of SPARE (SPray Air Requirement)  AWARE definition at 20°C and 10 5 Pa For use at elevated temperature correction factor  For ventilation of 1 m 3 working space AWARE 1 used as input for calculation of workspace ventilation using a near field - far field approach (under development!)

developments…… 2.Operationalisation default values for use in AWARE  Default risk factor f/OEL replaced by more comprehensible default OEL - in case of non-existing OELs - alternative approach for default setting allowed: for example read across or kick-off limit value procedure  Check on defaults for monomer content of binders - advise on reduction of default for epichlorohydrin in epoxy (0.1%) - justification of other defaults  Acceptance of not-using R45 (may cause cancer) for mineral spirit fractions

developments…… 3.Validation of the AWARE 1  Relation of AWARE 1 with VOC content product - no correlation established  Validation AWARE 1 under standard exposure conditions - regression coefficient R 2 = 0,86, i.e. good correlation of AWARE 1 and workplace concentration: High AWARE 1 high exposure  Validation with actual workplace measurements - presentation Heusen : good correlation

Relation of AWARE 1 with VOC content product Polynomial fitLinear fit

developments…… 3.Validation of the AWARE 1  Relation of AWARE 1 with VOC content product - no correlation established  Validation AWARE 1 under standard exposure conditions - regression coefficient R 2 = 0,86, i.e. good correlation of AWARE 1 and workplace concentration: High AWARE 1 high exposure  Validation with actual workplace measurements - presentation Heusen : good correlation

Validation AWARE 1 under standard exposure conditions Exposure data as % OEL, its linear correlation with the AWARE 1 and the upper and lower 95% prediction intervals

developments…… 3.Validation of the AWARE 1  Relation of AWARE 1 with VOC content product - no correlation established  Validation AWARE 1 under standard exposure conditions - regression coefficient R 2 = 0,86, i.e. good correlation of AWARE 1 and workplace concentration: High AWARE 1 high exposure  Validation with actual workplace measurements - presentations Heusen and Krop : good correlation

developments…… 4. Comparison of the AWARE based on the analysed VOC composition with the SDS based AWARE

Solvents measured versus default SDS Metal protective coatings (Epoxy – PU)

Aware of protective epoxy coatings based on the SDS and the analysed VOC content

developments…… update basis report The AWARE code Adequate Warning and Air Requirement A code for risk assessment of, and hazard communication on products containing volatile organic compounds Hildo Krop, Pieter van Broekhuizen, Fleur van Broekhuizen IVAM, Amsterdam, October 2007, Version 2.0

developments…… User friendly web based tool for the calculation of the AWARE Development in final stage Foreseen Internet address:

AWARE ready-for-use product calculation screen