A Critical Review of Indoor Formaldehyde

Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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ED A CRITICAL REVIEW OF INDOOR
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FORMALDEHYDE
CONCENTRATIONS AND
AT
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Prof. Dr. T. Salthammer
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Fraunhofer WKI
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Department of Material Analysis & Indoor Chemistry
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Braunschweig, Germany
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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TOPICS
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 Formaldehyde
basics
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 Formaldehyde
application
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 FormaldehydeLindoor
AN concentrations
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 Formaldehyde tropospheric
SC chemistry
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 From indoor towards outdoor?
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 Formaldehyde air quality guidelines
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 Summary and Conclusion
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0.1 ppm = 100 ppb = 125 µg/m³
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE: PHYSICAL AND CHEMICAL PROPERTIES
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Structure
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AL
CAS registry no.
50-00-0
Molecular formula
HCHO, CH2O
Molecular weight
30.03 g/mol
ANMelting point
D
Spoint
Boiling
CI
E
Dipole moment N
-92 °C
a
Solubility
-21 °C
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2.33 D
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soluble in water, ethanol, ether, acetone
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Henry’s law constant
2.5 103 M/atm (25 °C)
log(Kow) b
-0.83
kOH
9.37  10-12 cm3 molecule-1 s-1 (298 K)
kO3
2.09  10-24 cm3 molecule-1 s-1 (298 K)
kNO3
5.80  10-16 cm3 molecule-1 s-1 (298 K)
Salthammer et al. (2010) Chemical Reviews
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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INDUSTRIAL APPLICATION OF FORMALDEHYDE
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Salthammer et al. (2010) Chemical Reviews
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE BASED RESINS FOR WOOD-BASED MATERIALS
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urea-formaldehyde-resin
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melamine-formaldehyde-resin
phenol-formaldehyde-resin
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE SOURCES
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HCHO
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Processing
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Product
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free HCHO
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outdoor air
Temperature
Humidity
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NTin
HCHO
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indoor air FIC
Ozone
VOCs
Product
Salthammer et al. (2010) Chemical Reviews
back reaction
combustion
biogenic
PUreactions
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE EMISSION FROM EXHALED BREATH GAS
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1,6
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AN
D
HCHO (ppb)
1,2
1,0
0,8
0,6
0,4
0,2
0,0
0
10
20
30
t (min)
Riess et al. (2010) Analytica Chimica Acta
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HCHO (acac method, ppb)
consumption of alcohol
1,4
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40
5
4
3
2
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smoking 2 cigarettes
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cigarette smoking
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1
0
0
10
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20
time (min)
30
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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BUILDING AND CONSUMER PRODUCTS MAY RELEASE FORMALDEHYDE
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









U
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Particleboard
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Fiberboard
NA
Insulation Materials
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ND
Furniture
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Paint
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NT
Paper
IFI
Air freshner (in the presence of ozone)
C
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Cosmetics
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Cigarettes (and other combustion sources)
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etc……..
Salthammer et al. (2010) Chemical Reviews
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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UNEXPECTED FORMALDEHYDE EMISSION: PHOTOCATALYTIC WALL PAINT
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100
A
Concentration (µg/m3)
90
80
70
Photocatalytic paint (P3)
Formaldehyde
Acetic aldehyde
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NA
60
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ND
50
light off
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light on
40
IFI
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30
20
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10
0
40
60
80
100
120
time (h)
Salthammer and Fuhrmann (2007) ES&T
140
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180
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE TEST METHODS
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48 m³ chamber
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N
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AN
D
1 m³ chamber
Salthammer et al. (2010) Chemical Reviews
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE: RESULTS OF GERMAN ENVIRONMENTAL SURVEYS
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UNDER
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U300
CA German Environmental Survey
TIO 1985-86 (N = 329)
250
NA
2003-06 (N = 586)
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200
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150
NT
IFI
100
C
formaldehyde
(µg m -3 )
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50
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0
P-10
P-50
P-90
P-95
P-98
Parameter
Salthammer et al. (2010) Chemical Reviews
GM
AM
Max
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE: STEADY STATE CONCENTRATION IN GERMAN HOMES
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25
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20
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N (%)
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Formaldehyde in private dwellings
367 data (1996-2006)
lognormal fit curve
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10
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5
0
0.05
0.10
0.15
HCHO (ppm)
Salthammer et al. (2010) Chemical Reviews
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0.20
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0.25
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE: MONTE-CARLO-SIMULATION (10000 runs)
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18 U
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Density (%)
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TIO
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log-normal fit curve
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10
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SER A  L
Cs 
n
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SERA = 30 µg/(m² h) (30 µg/m³ = 25 ppb)
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L = 0.5 – 1.5 m²/m³ (uniform distribution)
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n = 0.05 – 0.95 h-1 (uniform distribution)
4
2
0
0
50
100
150
200
HCHO (ppb)
Salthammer (2011) Chemosphere
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300
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350
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE AND AIR EXCHANGE
F(extracted from the 1996-2006 steady state concentrations)
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0.20
AT
0.15
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HCHO (ppm)
OR
0.10
0.05
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AN
D
0.00
1.0
1996
SC
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2001
air exchange (h-1 )
0.8
0.6
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2006
IFI
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0.4
0.2
0.0
1996
Salthammer et al. (2010) Chemical Reviews
2001
2006
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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EMISSION AND EXPOSURE
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Emission
source
Emission
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Living
behavior
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Indoor
Air
pollution
Exposure
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Climatic
conditions
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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WKI/EURIMA TEST HOUSE STUDY
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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RESULTS OF FORMALDEHYDE MEASUREMENT ( n = 0.3 h-1 inside the house)
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D
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Salthammer et al. (2010) Chemical Reviews
Salthammer and Mentese (2008) Chemosphere
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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INDOOR FORMALDEHYDE: SUMMARY OF INTERNATIONAL STUDIES (in ppb)
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AT
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N
25
17
17
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34
AN
20
28
D 23 10 56
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IF
20
27
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blue: median (50-P)
green: geometric mean
red: arithmetic mean
Data: from Salthammer et al. (2010) Chemical Reviews and WHO (2010)
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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500 MILLION PEOPLE LIVE IN THE 30 BIGGEST MEGACITIES
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Picture: http://www.wikipedia.de
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE AS A SECONDARY POLLUTANT FROM OZONE REACTION
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Criegee (1975) Angew. Chem. Int. Ed., 14, 745
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMATION OF FORMALDEHYD BY ISOPRENE/OH/NO REACTION
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Carter and Atkinson (1996) Int. J. Chem. Kin. 28, 497
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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CONCENTRATION OF NMHCS UND CARBONYLS IN BEIJING (SUMMER 2006)
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concentration in ambient air (µg/m³)
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Formaldehyde
35
AT
30
25
20
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n-Hexane
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(VOC) = 264 µg/m³ (N = 69)
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15
10
5
0
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n-Pentane
Propane
n-Undecane
Ethan
Methylcyclohexane
Alkanes
Ethene
Acetylene
Propene
Isoprene
-Pinene
Alkenes
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IFI
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Toluene
Mesitylene
arom. HC
compound class
Duan et al. (2008) Atmospheric Research 88, 25-35
Acetaldehyde
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m,p-Xylene
Benzene
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Hexanal
Benzaldehyde
Carbonyls
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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FORMALDEHYDE: FROM INDOOR POLLUTANT TO OUTDOOR POLLUTANT?
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39
D
SC
14
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IF
27
22
IC
113
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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BIOFUEL COMBUSTION PRODUCES CARBONYL COMPOUNDS
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The increased use of biofuel will increase the Pformaldehyde
concenUR
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tration in ambient air.
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Kohse-Höinghaus et al. (2010) Angewandte Chemie Int. Ed.
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
INTERNATIONAL INDOOR AIR FORMALDEHYDE GUIDELINES
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Indoor Guideline (ppm)
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E0.10
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Korea (8h)
UC Germany (confirmed 2006)
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Japan (0.5h)
UK (0.5h)
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0.08
Austria (8h)
ALshort term 2010) China (1h) Australia
WHO (long and
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0.06
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0.04
Canada (8h)
Poland (24h)
IFI
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Hong Kong (8h) P
UR
0.02
PFrance
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California (chronic REL)
0.00
1977
1990
1995
2000
2005
2010 ON
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Year
Salthammer (2011) Chemosphere (modified)
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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DECREASING GUIDELINES AND INCREASING OUTDOOR VALUES OVERLAP
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0.09
0.08
HCHO (ppm)
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0.00
AT
Decreasing indoor guidelines
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Correa et al. (2005), Rio de Janeiro - 113 ppb
Khoder et al. (2000), Cairo - 39 ppb mean
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Duan et al. (2008), Beijing - 27 ppb during summer smog
Bakeas et al. (2003), Athens - 14 ppb
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FORMALDEHYDE ANALYTICS
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acetyl acetone
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A
DNPH
O
O
2
TIO
O2N
Color Test
O
O
+ HCHO + NH3
-3 H2O
N
H
NA
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NH-NH2 +
NO2
R1
R1
C=O
ND
R2
-H2O
O2N
NH-N=
SC
NO2
R2
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N
TIF
DNPH and acetyl acetone method (online or discontinuous)
are
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suitable for the indoor related analysis of formaldehyde.
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The PTR-MS method (m/z 31) can not be recommend for the analysis
of formaldehyde (especially in humid environment like breath gas).
Schripp et al. (2010) International Journal of Mass Spectrometry
Salthammer and Mentese (2008) Chemosphere
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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false negative
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false positive
5%
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85%IO 15%
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NA
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14
Density (%)
color reaction (Y/N decision) with 95% reliability
5%
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20
12
ND
How high is the probability of the guideline
value actually being exceeded when the
detector tube shows this?
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Bayesian approach:
10
NT
1
IFI 1

 0.77
0
.
05

0
.
85
P
(
B
/
A
)

P
(
A
)
1
1 C
0.95  0.15
P(B P
/ AU
)  P( A )
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P( A / B) 
8
6
4
2
0
0
50
29
100
150
200
HCHO (ppb)
Salthammer (2011) Chemosphere
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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MEANING OF A GUIDELINE FROM THE STATISTICAL POINT OF VIEW
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If aRlog-normal distribution is assumed for room air concentrations, it
hardlyEmakes
DU sense from the statistical point of view to demand global
complianceCwith
A a guideline value.
TIO
NA
20
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18
16
ND
Density (%)
14
12
10
log-normal fit curve
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8
6
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IFI
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4
2
0
0
50
100
150
200
HCHO (ppb)
250
300
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In principle all that the guideline value states is the percentage
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exceedances which is acceptable!
Salthammer (2011) Chemosphere
Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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Question 1:
RIs the lower guideline always the better guideline ?
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L“The
ANend justifies the means”
N. Machiavelli
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Question 2:
Does the benefit always justify the effort ?
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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IS THE LOWER INDOOR GUIDELINE ALWAYS THE BETTER GUIDELINE ???
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Cost
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Benefit
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time
Salthammer (2011) Chemosphere
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Guideline
low
high
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INDOOR AND OUTDOOR FORMALDEHYDE CONCENTRATION RANGES
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Salthammer et al. (2010) Chemical Reviews
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
SUMMARY AND CONCLUSION
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 Industrial
chemistry is needed to improve the quality of life for seven billion
E
peopleDon this planet.
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 Formaldehyde
ATis an important feedstock for building and consumer products,
but…..
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A an important indoor pollutant.
 …..formaldehyde is also
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 In the indoor environment the
NDformaldehyde concentrations are continuously
decreasing (median or GM usually
S20 – 40 ppb).
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 A long term a short term indoor guideline
IE value of 0.08 ppm as derived by the
WHO is scientifically sound and realistic.NT
IFI
 I reasonably doubt that indoor guidelines in theC
range of 10 ppb are needed
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and sustainable.
R increasing in urban
 Formaldehyde outdoor concentrations are continuously P
O
environments as a consequence of atmospheric air pollution. S
ES
 Is formaldehyde turning from an indoor pollutant towards an outdoor
ONpollutant?
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Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
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8th European Wood-Based Panel
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Symposium
2012
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•
•
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Date:
Location:
TIO 10.-12.10.2012
NHannover,
Maritim Airport Hotel
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Thank
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A
L A for Your Attention
You
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