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