Download - Technical lessons and improvements to the AWARE code Conference on Product Codes within REACH
Technical lessons and improvements to the AWARE code
Conference on Product Codes within REACH
Gent, 4 and 5 OctoberPieter 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/m3 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 Pi eq > 30.000 the evaporation is instanteous
Risk approach: Margin of Safety
Exp
OEL
C
CMoS
i
OELi
wsi
OELmix
wstot
P
P
C
CMoS
1
Margin of Safety:
AWARE1 approach:
OELC Concentration Occupational Exposure Limit
ExpC Exposure concentration
wstotC Total airborne concentration volatiles at workplace
OELmixC Combined OELs volatiles
iP Vapour pressure component i
1
1
Final AWARE1
i i
eqii
i i
ii
OEL
Pcd
OEL
fcdAWARE
3
100001
AWARE1 = is defined as the amount of fresh air (m3), required to ventilate 1 m3 of the working space, to dilute the evaporated volatiles after applying 1 liter of solvent containing product, at a room temperature of 20C and an atmospheric pressure of 105 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 (m3) 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)ci = mass percentage of the solvent ‘i’ in the product (% (m/m))
fi = evaporation factor of solvent ‘i’ (0 ≤ fi ≤ 1) = Pieq/30.000
Pieq = equilibrium vapour pressure of component i at room temperature (Pa)
OELi = Occupational Exposure Limit of solvent ‘i’ (mg (solvent) m-3 (air))
AWARE2 code numbers
AWARE2 = Indicator for identified hazards of the product
1. Different toxic effects
(corrosivity, allergenicity, carcinogenicity etc)
2. R-phrase according to Dangerous Preparation Directive
3. AWARE2 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 AWARE2
AWARE 2 coding
R-phrase*
(Ready-For-Use-Product) AWARE2
Code numbers Indicative significance **
None of the R-phrases mentioned below.
I Products with no or a very low potential hazardous effect
R20, R21, R22, R65, R68/20/21/2, R48/20/21/22, R62, R63, R66, R36/37/38
II Products that contain harmful or irritating components for all exposure routes.
R23, R24, R25, R39/23/24/25 R34, R41, R33, R40, R64, R68 Ph < 2,0; pH > 11,5 R29, R31, H+OEL (no R-phrase)
III
Products containing components that are toxic to all exposure routes or corrosive. These components may also cause serious irreversible effects.
R26, R27, R28, R32 R39/26/27/28, R60, R61 R35, R48/23/24/25,R43, R42
IV
Products with components that are very toxic, very corrosive or allergenic, or that may cause serious irreversible effects. Chronic exposure is a risk for serious health damage.
R45, R46, R49 V
Products with components that are mutagenic or are carcinogenic.
* A list of R-phrases is given in Annex IV ** The ready-for-use product may be the labeled with other R-phrases like for example reproductive toxic effects. These
effects are classified under codes –II, -III, and –IV as well.
AWARE code Based on the Ready-For-Use product Potential risk indicator with two digits:
AWARE1 - AWARE2
What developments in AWARE since 2006 ?
1. Fine tuning definition AWARE
AWARE restricted to manual application. For spraying application AWARE1
development of SPARE (SPray Air Requirement)
AWARE definition at 20°C and 105 Pa For use at elevated temperature
correction factor
For ventilation of 1 m3 working space AWARE1 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 AWARE1
development of SPARE (SPray Air Requirement)
AWARE definition at 20°C and 105 Pa For use at elevated temperature
correction factor
For ventilation of 1 m3 working space AWARE1 used as input for calculation of workspace ventilation using
a near field - far field approach (under development!)
Vapour pressure multiplication
factors for elevated temperature
Vapour pressure multiplication factor
Substance P (20C)
(Pa) 20 30 C
20 40 C
20 50 C
20 60 C
20 70 C
20 80 C
Xylene 800 1,8 3,1 5,1 8,2 12,9 19,7 Ethylbenzene 930 1,8 3,0 5,0 8,0 12,5 19,0 Solvent-nafta 80 1,7 2,9 4,8 7,6 11,6 17,5 Methoxypropylacetate 510 1,8 3,2 5,4 8,8 13,9 21,5 n-butylacetate 1070 1,8 3,2 5,3 8,7 13,8 21,4 isobutanol 1700 2,0 3,7 6,7 11,8 19,9 32,7 methylisobutylketon 700 1,8 3,1 5,2 8,4 13,2 20,2 1-methoxypropane-2-ol 1080 1,9 3,5 6,3 10,8 17,9 28,9
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 AWARE1
development of SPARE (SPray Air Requirement)
AWARE definition at 20°C and 105 Pa
For use at elevated temperature correction factor
For ventilation of 1 m3 working space AWARE1 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 AWARE1
Relation of AWARE1 with VOC content product- no correlation established
Validation AWARE1 under standard exposure conditions - regression coefficient R2 = 0,86 , i.e. good correlation of
AWARE1 and workplace concentration:
High AWARE1 high exposure
Validation with actual workplace measurements- presentation Heusen : good correlation
Relation of AWARE1 with VOC content product
Epoxy coatings
R2 = 0,31
0
50
100
150
200
10 15 20 25 30 35
mass% VOC
Epoxy coatings
trend line freeR2 = 0,08
Trend line through originR2 = -0,60
0
50
100
150
200
10 15 20 25 30 35
mass% VOC
Polynomial fit Linear fit
developments……
3. Validation of the AWARE1
Relation of AWARE1 with VOC content product- no correlation established
Validation AWARE1 under standard exposure conditions - regression coefficient R2 = 0,86 , i.e. good correlation of
AWARE1 and workplace concentration:
High AWARE1 high exposure
Validation with actual workplace measurements- presentation Heusen : good correlation
Validation AWARE1 under standard exposure conditions
A5
A3 A1
A4
B1
A2B4
B2B8
B7B9
B6B5
B3A6
0
50
100
150
200
0 5 10 15 20 25
AWARE code
Ex
po
su
re (
%O
EL
)
Exposure data (%OEL)upper 95% PI line of AWARE trendlineAWARE trendlinelow er 95% PI line of AWARE trendline
Exposure data as % OEL, its linear correlation with the AWARE1
and the upper and lower 95% prediction intervals
developments……
3. Validation of the AWARE1
Relation of AWARE1 with VOC content product- no correlation established
Validation AWARE1 under standard exposure conditions - regression coefficient R2 = 0,86 , i.e. good correlation of
AWARE1 and workplace concentration:
High AWARE1 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
Fig 6.5 Total solvent content of the 15 metal protecting coatings selected (orange/left) based on the SDS information and (green) determined experimentally based on VOC analysis.
0
10
20
30
40
50
60
70
80
90
100
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Products
m/m
%
Solvents MSDS Solvents analysis
Metal protective coatings (Epoxy – PU)
Aware of protective epoxy coatings based on the SDS and the analysed VOC content
0
20
40
60
80
100
120
140
160
1 5 6 7 9 10 11 12 14
Coating
AW
AR
E-1
AWARE1 SDS AWARE1 VOC
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:
www.awaretool .eu
www.awarecode.eu
AWARE ready-for-use product calculation screen