ivam research and consultancy on sustainability1 aware code adequate warning and air requirement a...
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IVAM research and consultancy on sustainability 1
AWARE codeAdequate 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 sustainability 2
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 sustainability 3
This presentation
•Part I • Background and AWARE1 derivation
• Comparison AWARE1 vs OAR/MAL1
•Part II• AWARE1 code for spraying and AWARE2 code
• Part III• AWARE code results and comparisons
IVAM research and consultancy on sustainability 4
Background AWARE
AWARE1 derivation
and
Comparison AWARE1 versus OAR/MAL1
Part I
IVAM research and consultancy on sustainability 5
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 sustainability 6
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
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Resulting AWARE code• Based on the Ready-For-Use product• Potential risk indicator with two digits:
AWARE1 - AWARE2 for example:
AWARE1 (850) = the volume of fresh air (m3) required to dilutethe air in the working space after the use of 1 L of the product to concentrations below the level of the combined OELs
AWARE2 (IV) = Indicator for identified hazards of all components
of the product
850 – IV
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Derivation of the AWARE1
Margin of Safety
expousre
OEL
tC
CtMoS
)()(
ij
OELj
wsj
jiOEL
i
wsi
OELmix
wstot
sC
sC
P
P
C
CMoS )(
)(1
Kinetic approach:
Static approach:
Assumptions1. No toxic interaction of components (additivity of effects)2. Distinction between exposure to volatile and non-volatile substances3. Volatile toxic interaction non-volatile toxic interaction
IVAM research and consultancy on sustainability 9
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
• AWARE1 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 sustainability 10
AWARE1 versus OAR and MAL1
i i
eqii
i i
ii
OEL
Pcd
OEL
fcdAWARE
3
100001
Differences between AWARE and OAR/MAL
• f is dimensionless and defined as ~ Peq/30 000
• Pieq,max is limited by a maximum based on V of 1 L
• for Pieq > 30.000Pa f =1
• More realistic (Gliding scale) evaporation factor f
• AWARE1 <(<) OAR or MAL1
• AWARE1 relatively more favourable for liquids with low Peq
AWARE1 is air requirement just above the liquid film
IVAM research and consultancy on sustainability 11
AWARE1 vs OAR/MAL1
Equilibrium
vapor pressure
Pa (20 °C)
Evaporation factor f
OAR/MAL1 approach
Evaporation factor f AWARE-code
10 0 0
10< pv 133 0.3 0.0003 – 0.004
133< pv 400 0.7 0.004 – 0.13
400< pv 1333 1.0 0.013 – 0.04
1333 < pv 26660 1.4 0.04 – 0.89
pv > 26660 2 0.89 - 1
Substance
(All d = 1)
Peq
(Pa)
OEL
(mg/m3)
% (m) in product
OAR
(m3/L)
AWARE
(m3/L)
Toluene 2800 150 10 933 62
Hypothetic 25000 150 10 933 555
Acetone 24700 1210 10 117 68
IVAM research and consultancy on sustainability 12
Other aspects in the AWARE1
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 forcomposition and mass range used
PART II
AWARE1 code for spraying and
AWARE2 code
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AWARE1 code for spraying (I) Evaporation rate droplets of volatile substances much higher than brush
application surface area A of droplets much larger Peq higher due to Kelvin effect
(Radius droplets decrease (A) but rate due to Peq )
Toxicological effects volatile fraction differs from non-volatile fraction
Contribution of respirable fraction of non-volatile substances Depends on gun spraying efficiency, SE (default 50%)
10% of the non-deposited fraction available for inhalation = {0.1*(1-SE)}
Ej
j
j
volatilenonspray S
sOEL
10000scdAWARE
1*1.0
)(
)(,1
IVAM research and consultancy on sustainability 15
AWARE1 code for spraying (II)
Contribution volatile fraction to AWARE1
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, SE (default 50%)
Final value for the AWARE1 code for spraying application is determined by: the largest value of the volatile or the non-volatile
i i
iiE
volatilespray OEL
cdfSAWARE
10000**)11(,1
IVAM research and consultancy on sustainability 16
AWARE2 code numbers
1. Different toxic effects not included in the AWARE1
(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
systems (IT-score, GWF, SOMS, ILO, MAL-2)
2. R67 not included in the AWARE2
IVAM research and consultancy on sustainability 17
Comparison AWARE2 and MAL2
AWARE2 5 classes – MAL2 7 classes
MAL: adds all (toxic) substances in the same class to determine MAL2
AWARE: the most toxic component determines the AWARE2
(slight) differences in limit weight percent
IVAM research and consultancy on sustainability 18
PART III
AWARE code calculations and
comparisons
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AWARE – calculation Metalcoating paint
CAS-nr Mass Mol.mass Pieq OEL f/OEL R-phrases Result
(%) (g/mol) (Pa) (mg/m3) (-) (from list & user input) Brush Spray (50%) OAR/MAL1
7779-90-0 8,73 0 0 R50/53 0 1296 01330-20-7 25,00 106,2 800 210 1,27E-04 R20;R21;R38; 47 907 176264742-95-6 0,87 127 200 100 6,67E-05 R65; 1 65 9090-72-2 1,27 265 3 0 R22;R36;R38; 0 188 0
29,52 0 5 0 0 4381 0106-89-8 0,07 92,5 1700 2 2,98E-02 R45;R23;R24;R25;R34;R43; 29 270 71425068-38-6 21,83 0 0 0 3240 071-36-3 11,90 74,1 700 45 5,19E-04 R22;R37;R38;R41;R67; 92 2008 391495-63-6 0,87 120,2 210 100 7,00E-05 R20;R36;R37;R38; 1 65 90
Total 170 9000 6571Density 1,48 kg/dm³ Brush Spray (50%)
(m3 air/dm3 product) 170 - IV(m3 air/dm3 product) 6571 -5
1-butanol (ONLT TWA of 15 min of 45 mg/m3)
1,2,4-trimethylbenzene
Application
Substance
xylene (isomer mixturel)
white spirit high aromatic Bp 166-185 oC
tris(dimethylaminomethyl)phenol
Zinc phosphate
Ready For Use ProductOAR/MAL code
brush/rollerAWARE code
Not identified solids
epichlorohydrine
Binder - BISPHENOL A COPOLYMER
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AWARE calculationFurniture Lacquers, brush/roller application
Fig 11.4 AWARE-code furniture lacquers, brush/roller application
0
50
100
150
200
250
300
350
II
II
II
IIIII
II
II
II
II
IV IV IV
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AWARE calculations
MAL1.2 and AWARE1,2 comparison paints(full and MSDS formulation)
I
IVIV
I I
5
51
1
3
0
50
100
150
200
250
Metal Epoxy Epoxy Highsolid
St. Alkyd woodpaint
St. water-based
styrene-acrylate
PUR-acrylatedispersion
(wood)
Type of paint
AW
AR
E1
cod
es
050010001500200025003000
MA
L1
valu
es
AWARE-1 recipe
AWARE-1-MSDS
MAL-1
High Peq, very low OEL and below VIB limit
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AWARE calculations
AWARE1 codes for spraying
0
4000
8000
12000
16000
Metal Epoxy Epoxy Highsolid
St. Alkydwood paint
St. water-based
styrene-acrylate
PUR-acrylatedispersion
(wood)
Type of paint
AW
AR
E1
cod
e
AWARE-1-recipe
AWARE-1-MSDS
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AWARE calculations
MAL1 and AWARE 1 comparison cleaning agents (full and MSDS formulation)
0 0 0
10 10
0 0 0 0 00
468 468
900
1080
0
2
4
6
8
10
12
1 2 3 4 5
Cleaning agent
AW
AR
E1
va
lue
0
200
400
600
800
1000
1200
MA
L1
va
lue
AWARE1-recipe
AWARE1-MSDS
MAL-1
IVAM research and consultancy on sustainability 24
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
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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 sustainability 26
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 sustainability 27
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