ivam research and consultancy on sustainability1 aware code adequate warning and air requirement a...

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


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+


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


Background AWARE

AWARE1 derivation

and

Comparison AWARE1 versus OAR/MAL1

Part I


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


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


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


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


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


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


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


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


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


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


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


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


PART III

AWARE code calculations and

comparisons


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


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


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


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


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


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


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


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

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