23/09/2013

EMISSIONS, EXPOSURE PATTERNS and HEALTH EFFECTS of

CONSUMER PRODUCTS in the EU

Consumer product emission testing; summarizing conclusions M. Stranger1, F. Maes1, E. Goelen1, E. Tolis2, J. Bartzis2,

P. Wolkoff3, A. Nörgard3, E. de Oliveira Fernandes4, G. Ventura Silva4

1Air Quality Measurements, Environmental Risk and Health, VITO 2Department of Engineering and Management of Energy Resources, University of West Macedonia, UOWM 3Indoor Environment Group, National Research Centre for the Working Environment, NRCWE 4Unit of Advanced Studies on Energy in the Built Environment, Instituto de Engenharia Mecânica, IDMEC

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Objective of emission testing in EPHECT

- To quantify emissions whilst simulating ‘real-life’ use scenarios

- harmonized emission test scenario’s

- repeatable/reproducible test protocols -> comparability of results

- max. fit with international standards for building/furnishings/product testing

- evaluations of similar experiments in rooms with different dimensions (small rooms – large rooms – real environments)

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EPHECT product classes

All purpose cleaners

Kitchen cleaning agents

Floor cleaning agent

Glass and window cleaner

Bathroom cleaning agents

Furniture polish

Coating products

Floor polish

Combustible air fresheners

Air fresheners (spray)

Passive air fresheners

Electric units

Hair styling products

Deodorants

Perfumes

Cleaning Agents Air fresheners Personal care products

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Market study on uses and use scenarios in the EU

81%

77%

77%

75%

72%

65%

60%

48%

41%

37%

35%

26%

22%

20%

20%

14%

All purpose cleaners

Bathroom cleaning products

Kitchen cleaning products

Glass and window cleaners

Perfumes

Floor cleaner

Spray deodorants

Air fresheners in sprays

Hairspray

Insecticides

Furniture polish

Combustible air fresheners

Electric air fresheners

Passive air fresheners

Coating products for leather and textiles

Floor polish

Q. R1. In the past 6 months, which of the following products have you personally used in your household? (Several answers possible)

High penetration

Medium penetration

Low penetration

Total: 4335 interviews

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EPHECT product classes

All purpose cleaners Liquid Flask

Kitchen cleaning agents Liquid Flask

Floor cleaning agent Liquid Flask

Glass and window cleaner Liquid Spray

Bathroom cleaning agents Liquid Spray

Furniture polish Liquid Flask

Coating products Liquid Flask

Floor polish Liquid Flask

Combustible air fresheners Solid Combustible

Air fresheners (spray) Liquid Spray

Passive air fresheners Solid To be volatilized

Electric units Liquid To be volatilized

Hair styling products Liquid Spray

Deodorants Liquid Spray

Perfumes Liquid Spray

Cleaning Agents Air fresheners Personal care products

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EPHECT Umbrella for product testing

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15 product classes 25 products :

-13 cleaning agents - air fresheners - 5 personal care products

EU most used + other most used

EPHECT key and emerging pollutants

CO - NO2 - ammonia - benzene - toluene - xylenes - Styrene – Phthalates -Lead - O3 - PAHs - Naphthalene - PCBs -PCDDs - chloroamines - hypochlorite - H2O2 - formaldehyde - acrolein - glutaraldehyde - acetaldehyde - siloxanes - fluorinated - quaternary ammonium chlorides - ozone consuming compounds : limonene - alpha-pinene - geraniol - a-terpineol - linalool - specific airway allergens: isocyanates - acid anhydrides - radical production - Particles (fine & ultrafine): - ultrafines PM < 0.1 - number - size area - chem. charact. - metals carbon origin (EC/OC) - oxidized PAHs (index 2005, WHO air quality guidelines, SCHER, selected emerging pollutants)

QA/QC

20.24 m³

0.916 m³

0.225 m³

0.0509 m³

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EPHECT Lab testing: total hydrocarbon THC deodorant spray, 1 spray in 1 m³; 0.5/h

Time

Concentr

ation

[ppm

]

THC glass and window cleaner, 1 spray in 1 m³; 0.5/h

Concentr

ation [ppm

]

Time

THC passive air freshener; 1 unit in 1 m³; 0.5/h

Time

Concentr

ation [ppm

]

Time

Concentr

ation

[ppm

]

THC electrical air freshener; 1 unit in 1 m³; 0.5/h

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EPHECT Lab testing: particulate matter

Particulate Matter emissions from a deodorant spray

Co

nc

en

trati

on

[µ

g/m

³]

Time [h]

Particulate Matter emissions from a candle

extinction lighting spray

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EPHECT Lab testing: VOC screening

Compound CAS conc [µg/m³] Explicitely in AgBB AgBB group name Contact allergen Carcinogens

match too low (rt 21,48) 124 semi-quant.

Dihydromyrcenol 18479-58-8 78,4 semi-quant.

Tripropylene glycol monomethylether 20324-33-8 49,3 semi-quant.

Diisobutylcarbinol 108-82-7 36,7 semi-quant.

match too low (rt 25,44) 31,3 semi-quant.

Linalyl acetate 115-95-7 29,2 semi-quant.

cyclohexanone,5-methyl-2-(1-methylethyl)- 491-07-6 26,0 semi-quant.

benzene,1-methyl-3-(1methylethyl)- 535-77-3 19,7 semi-quant. X

Eucaliptol 470-82-6 12,0 quant.

Limonene 138-86-3 11,7 quant.* X X

β-Pinene 127-91-3 9,2 quant. X

Linalool 000078-70-6 8,5 quant.* X

cyclohexanol,5-methyl-2-(1-methylethyl)-,(1.alpha.,2.beta.,5.alpha)-(+/-) 2216-51-5 8,2 semi-quant. Terpene, sonstige

α-pinene 80-56-8 5,8 quant.* X

γ-Terpinene 99-85-4 4,6 semi-quant. Terpene, sonstige

toluene 108-88-3 3,8 quant. X

1,3,7-octatriene,3,7-dimethyl- 502-99-8 3,6 semi-quant. Terpene, sonstige

camphene 79-92-5 2,3 semi-quant. Terpene, sonstige

beta-phellandrene 555-10-2 2,1 semi-quant. Terpene, sonstige

hexanal 66-25-1 1,6 semi-quant. X

3 - Carene 498-15-7 1,0 quant. X

alpha-phellandrene 99-83-2 0,6 semi-quant. Terpene, sonstige

1-hexanol 111-27-3 0,1 semi-quant. X

2-propanol,1-butoxy- 5131-66-8 0,1 semi-quant. X

TVOC 769 semi-quant.

Passive air freshener – ideal room concentrations after 5 hours, 1 unit in 30 m³, 0.5/h

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EPHECT Lab testing: VOC screening

Compound CAS conc [µg/m³] Explicitely in AgBB AgBB group name Contact allergen Carcinogens

match too low (rt 21,48) 124 semi-quant.

Dihydromyrcenol 18479-58-8 78,4 semi-quant.

Tripropylene glycol monomethylether 20324-33-8 49,3 semi-quant.

Diisobutylcarbinol 108-82-7 36,7 semi-quant.

match too low (rt 25,44) 31,3 semi-quant.

Linalyl acetate 115-95-7 29,2 semi-quant.

cyclohexanone,5-methyl-2-(1-methylethyl)- 491-07-6 26,0 semi-quant.

benzene,1-methyl-3-(1methylethyl)- 535-77-3 19,7 semi-quant. X

Eucaliptol 470-82-6 12,0 quant.

Limonene 138-86-3 11,7 quant.* X X

β-Pinene 127-91-3 9,2 quant. X

Linalool 000078-70-6 8,5 quant.* X

cyclohexanol,5-methyl-2-(1-methylethyl)-,(1.alpha.,2.beta.,5.alpha)-(+/-) 2216-51-5 8,2 semi-quant. Terpene, sonstige

α-pinene 80-56-8 5,8 quant.* X

γ-Terpinene 99-85-4 4,6 semi-quant. Terpene, sonstige

toluene 108-88-3 3,8 quant. X

1,3,7-octatriene,3,7-dimethyl- 502-99-8 3,6 semi-quant. Terpene, sonstige

camphene 79-92-5 2,3 semi-quant. Terpene, sonstige

beta-phellandrene 555-10-2 2,1 semi-quant. Terpene, sonstige

hexanal 66-25-1 1,6 semi-quant. X

3 - Carene 498-15-7 1,0 quant. X

alpha-phellandrene 99-83-2 0,6 semi-quant. Terpene, sonstige

1-hexanol 111-27-3 0,1 semi-quant. X

2-propanol,1-butoxy- 5131-66-8 0,1 semi-quant. X

TVOC 769 semi-quant.

Passive air freshener – ideal room concentrations after 5 hours, 1 unit in 30 m³, 0.5/h

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EPHECT Lab testing : VOC screening

Perfume – ideal room concentration (0-30 min.); 1 spray on cotton cloth in 30 m³; 0.5/h

Compound CAS conc [µg/m³] Contact allergen

7-Octen-2-ol, 2,6-dimethyl- 018479-58-8 7,3 semi-quant.

? Match factor too low (rt 24,9) 7,3 semi-quant.

Linalool 000078-70-6 3,5 quant. X

1,6-Octadien-3-ol, 3,7-dimethyl- 000078-70-6 3,4 semi-quant.

Limonene 138-86-3 2,2 quant. X

linalyl acetate 115-95-7 1,9 semi-quant.

? Match factor too low (rt 25,5) 0,9 semi-quant.

Geraniol 106-24-1 0,8 quant.* X

beta-pinene 000127-91-3 0,7 semi-quant.

β-Pinene 127-91-3 0,7 quant.

γ-Terpinene 99-85-4 0,0 semi-quant.

benzene,1-methyl-3-(1methylethyl)- 535-77-3 0,02 semi-quant.

2-Ethyl-1-hexanol 104-76-7 0,02 semi-quant.

1,3,7-octatriene,3,7-dimethyl- 502-99-8 0,02 semi-quant.

camphene 79-92-5 semi-quant.

1,6-Octadien-3-ol, 3,7-dimethyl-, 2-aminobenzoate 007149-26-0 semi-quant.

TVOC 31 semi-quant.

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EPHECT Lab testing : VOC screening

Compound CAS conc [µg/m³] Contact allergen

7-Octen-2-ol, 2,6-dimethyl- 018479-58-8 7,3 semi-quant.

? Match factor too low (rt 24,9) 7,3 semi-quant.

Linalool 000078-70-6 3,5 quant. X

1,6-Octadien-3-ol, 3,7-dimethyl- 000078-70-6 3,4 semi-quant.

Limonene 138-86-3 2,2 quant. X

linalyl acetate 115-95-7 1,9 semi-quant.

? Match factor too low (rt 25,5) 0,9 semi-quant.

Geraniol 106-24-1 0,8 quant.* X

beta-pinene 000127-91-3 0,7 semi-quant.

β-Pinene 127-91-3 0,7 quant.

γ-Terpinene 99-85-4 0,0 semi-quant.

benzene,1-methyl-3-(1methylethyl)- 535-77-3 0,02 semi-quant.

2-Ethyl-1-hexanol 104-76-7 0,02 semi-quant.

1,3,7-octatriene,3,7-dimethyl- 502-99-8 0,02 semi-quant.

camphene 79-92-5 semi-quant.

1,6-Octadien-3-ol, 3,7-dimethyl-, 2-aminobenzoate 007149-26-0 semi-quant.

TVOC 31 semi-quant.

Perfume – ideal room concentration (0-30 min.); 1 spray on cotton cloth in 30 m³; 0.5/h

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EPHECT Lab testing: TVOC

TVOC standard room concentration

[µg/m³ ]

Timing Operation (0.5 ACH)

Electrical air freshener 1 962* 300-330 min 1 air freshener, max position

Passive air freshener 769* 300-330 min 1 air freshener

Electrical air freshener 2 655* 300-330 min 1 air freshener, max position

Kitchen cleaning agent 512* 0-30 min mass applied on surface of 0.4 m²/m³

Candle 145 0-420 min burning one candle + extinguishment

Glass and window cleaner 103 0-30 min 1 spray / 30 m³

Air freshener spray 67 0-30 min 1 spray / 30 m³

Hair styling spray 43 0-30 min 1 spray / 30 m³

Deodorant women 38 0-30 min 1 spray / 30 m³

Perfume 31 0-30 min 1 spray on a cotton cloth / 30 m³

Deodorant men 26 0-30 min 1 spray / 30 m³

* Recommended evaluation standard German IRK/AOLG Ad-hoc Working Group, Level 2 - TVOC 0.3-1 mg/m³: ‘No relevant objections, provided that any guide values for individual substances or groups of substances are not exceeded’

Note: this table does not contain all studied products

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EPHECT Emission Rates Use and use scenario Emission Rate units Normalized Emission Rate units

Applied on a surface

all purpose cleaner

µg/h

(dilutions according to

manufacturer or market study)

Area specific emission rate

µg/(h.g.m2)

kitchen cleaning agent

floor cleaning agent

glass and window cleaner

bathroom cleaning agent

furniture polish

floor polish

Combustible, active or passive units

passive units

µg/h

Mass specific emission rate

µg/(h.g) electric units

combustible air fresheners

Sprayed on a surface or in the air

air fresheners (spray)

µg/h

(±0,5 sec or 0.5g automatic spray)

Mass specific emission rate

µg/(h.g aerosol)

(±0,5 sec or 0.5g automatic spray)

hair styling products

deodorants (sprays)

coating products (sprays)

perfumes

glass and window cleaner (spray)

ASTM 5116-10 – Standard Guide for small-scale environmental chamber determinations of organic emissions from indoor materials/products. Evaluation of VOC Emissions from building products, Sold Flooring material. ECA report 18, 1997. Influence of Air Fresheners on the Indoor Air Quality. Study ordered by the Federal Public Service of Helath; Food Chain Savety and Environment. M. Spruyt et al. 2006. Organic Indoor Air Pollutants; Occurence, Measurement, Evaluation, second edition. Tunga Salthammer and Erik Uhde. Wiley-VCH, Weinheim 2009. Standard ECMA-328 – Determination of chemical emission rates from electronic equipment, 5th edition 2010.

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EPHECT Emission Rates based on room concentrations (intercomparison)

Limonene specific emission rates

Perfume

Linalool specific emission rates

room size AER mass L SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

Perfume VITO 0,916 0,5 0,06 0,1 2.303 221 687 66 3.734 526

NRCWE 20,24 0,5 0,20 0,01 2.804 153 - - - -

IDMEC 0,255 0,86 0,07 0,3 1.098 157 694 55 6.110 476

UOWM 0,051 0,5 0,16 3,1 0,4 1,4 1,1 3,6 - -

Limonene β-pinene linalool

RSD 35% 18% 1% 10% 24% 5%

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EPHECT Emission Rates based on room concentrations

Specific Emission Rates of 2 different passive air fresheners

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EPHECT study of secondary reactions

- Passive air freshener, electrical air freshener, kitchen cleaning agent, studied in presence of ozone

- Secondary reaction products identified and quantified

- For certain terpene containing products, concern should be raised to both

acute effects and sensory irritation (eyes and upper airways).

- Acrolein reached close to 100% of its proposed LOAEL value for long-term effects for one experiment

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EPHECT Consumer product testing CONCLUSIONS

SER of priority compounds for all studied 25 products

Considerable different THC emission profiles in pattern and magnitude

Considerable different composition/emission of products in same product class

TVOCs levels may be in Level 2 of the German Guidance Value for TVOC

Relevant EPHECT priority compounds, but minor fraction of all emitted compounds

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EPHECT Consumer product testing CONCLUSIONS

Product testing use scenario’s with limited operational steps , better repeatability;

Loading factors sufficiently high

The smallest test chamber difficulties to assess terpene emissions from EPHECT products

Intercomparison provided valuable information on

- reproducibility of the product tests in test rooms with different dimensions

- repeatability of the use scenario (degrees of freedom)

- experimental limitations “what have we learned...”: guidance on emission

The EPHECT umbrella for consumer product testing provides a framework to harmonize

consumer product testing, yet more research on repeatability and reproducibility is

needed before standardisation of a protocol can take place.

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Thank you!