A Critical Review of Indoor Formaldehyde Concentrations Guideline Values by Tunga Salthammer

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.
2012 - Salthammer
FO
ED A CRITICAL REVIEW OF INDOOR UC FORMALDEHYDE CONCENTRATIONS AND AT IO GUIDELINE VALUES NA LA ND SC IE NT IFI C Prof. Dr. T. Salthammer PU RP Fraunhofer WKI OS Department of Material Analysis & Indoor Chemistry ES Braunschweig, Germany ON LY
Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer
FO
TOPICS R ED UC Formaldehyde basics AT IO Formaldehyde application NA FormaldehydeLindoor concentrations AN D Formaldehyde tropospheric chemistry SC IE NT From indoor towards outdoor? IFI C Formaldehyde air quality guidelines PU R Summary and Conclusion
PO
SE
0.1 ppm = 100 ppb = 125 g/m
ON
LY
FORMALDEHYDE: PHYSICAL AND CHEMICAL PROPERTIES
FO
ED
UC
Structure
AT
IO N
CAS registry no.
50-00-0 HCHO, CH2O 30.03 g/mol -92 C -21 C
AL
Molecular formula
ANMelting point D SC Boiling point IE Dipole moment N

a
Molecular weight
Solubility
TIF
2.33 D soluble in water, ethanol, ether, acetone 2.5 103 M/atm (25 C) -0.83
Henrys law constant log(Kow) b kOH kO3 kNO3
IC
PU
RP
9.37 10-12 cm3 molecule-1 s-1 (298 K) 2.09 10-24 cm3 molecule-1 s-1 (298 K) 5.80 10-16 cm3 molecule-1 s-1 (298 K)
OS
ES
ON
LY
Salthammer et al. (2010) Chemical Reviews
INDUSTRIAL APPLICATION OF FORMALDEHYDE
FO
ED
UC
AT
IO N
AL
AN
SC
IE
NT
IFI C
PU
RP
OS
ES
ON
LY
FORMALDEHYDE BASED RESINS FOR WOOD-BASED MATERIALS
FO
AT urea-formaldehyde-resin
ED
UC
IO N
AL
AN
SC
IE
melamine-formaldehyde-resin
NT
IFI C
PU
RP
OS
phenol-formaldehyde-resin
ES
ON
LY
FO
FORMALDEHYDE SOURCES
ED
HCHO
UC
Processing
AT
IO N
Product
free HCHO
AL
AN
Temperature
SC
Humidity
back reaction
outdoor air
N in HCHO T IFI indoor air C

Ozone
IE
combustion biogenic PUreactions RP OS
VOCs Product
ES
ON
LY
FORMALDEHYDE EMISSION FROM EXHALED BREATH GAS
FO
ED
UC
AT
IO N
AL
AN
1,6 1,4 1,2
SC
HCHO (acac method, ppb)
consumption of alcohol
IE
NT
5 4 3 2 1 0
HCHO (ppb)
1,0 0,8 0,6 0,4 0,2 0,0 0 10 20 30 40
smoking 2 cigarettes
IFI C
cigarette smoking
PU
RP
OS
20
ES
30
10
ON
40
t (min)
time (min)
LY
Riess et al. (2010) Analytica Chimica Acta
BUILDING AND CONSUMER PRODUCTS MAY RELEASE FORMALDEHYDE
FO
ED
CA Particleboard TIO Fiberboard NA Insulation Materials LA ND Furniture SC Paint IE NT Paper IFI Air freshner (in the presence of ozone) C PU Cosmetics RP Cigarettes (and other combustion sources) OS ES etc..
ON
LY
10
UNEXPECTED FORMALDEHYDE EMISSION: PHOTOCATALYTIC WALL PAINT
FO
ED110 UC 100 A
90 80 70 60 50 40 30 20 10 0 40
Concentration (g/m3)
TIO
Photocatalytic paint (P3) Formaldehyde Acetic aldehyde
NA
LA
ND
light off
SC
light on
IE
NT
IFI C
PU
RP
160
OS
60
80
100
120
140
180
ES
time (h)
Salthammer and Fuhrmann (2007) ES&T
ON
LY
11
FO
FORMALDEHYDE TEST METHODS
ED
UC
AT
IO N
48 m chamber
AL
AN
SC
IE
NT
IFI C
PU
RP
OS
ES
1 m chamber
ON
LY
12
FORMALDEHYDE: RESULTS OF GERMAN ENVIRONMENTAL SURVEYS FO UNDER NORMAL LIVING CONDITIONS
ED
formaldehyde
UC 300 AT German Environmental Survey IO 1985-86 (N = 329) 250 NA 2003-06 (N = 586) LA ND 200 SC IE 150 NT IFI 100 C
50 0 P-10 P-50 P-90 P-95 P-98 GM
(g m -3 )
PU
RP
OS
AM
Max
ES
Parameter
ON
LY
13
FO
FORMALDEHYDE: STEADY STATE CONCENTRATION IN GERMAN HOMES
ED
UC
20 15
25
AT
IO N
AL
Formaldehyde in private dwellings 367 data (1996-2006) lognormal fit curve
AN
N (%)
SC
10 5 0
IE
NT
IFI C
PU
RP
OS
0.05
0.10
0.15
0.20
0.25
ES
HCHO (ppm)
ON
LY
14
FO
FORMALDEHYDE: MONTE-CARLO-SIMULATION (10000 runs)
R 20 ED 18 U
16 14 12 10 8 6 4 2 0 0
CA
TIO
log-normal fit curve
NA
Density (%)
LA
ND
SER A L Cs n
SC
SERA = 30 g/(m h) (30 g/m = 25 ppb)

L = 0.5 1.5 m/m (uniform distribution) n = 0.05 0.95 h-1 (uniform distribution)
IE
NT
IFI C
PU
RP
OS
50
100
150
200
250
300
350
ES
HCHO (ppb)
Salthammer (2011) Chemosphere
ON
LY
15
FORMALDEHYDE AND AIR EXCHANGE (extracted from the 1996-2006 steady state concentrations) F
OR
ED
UC
0.20
HCHO (ppm)
AT
IO N
0.10 0.05 0.00
0.15
AL
AN
1.0
1996
SC
2001
IE
0.8
NT
2006
air exchange (h-1 )
IFI C
0.6
PU
0.4
RP
OS
0.2
ES
0.0
1996
ON
2001
2006
LY
16
EMISSION AND EXPOSURE
FO
ED
UC
AT
IO N
Living behavior
AL
AN
SC
Emission source
N Indoor T
Air
IE
IFI C
pollution
PU
RP
Climatic conditions
OS
ES
Emission
Exposure
ON
LY
17
FO
WKI/EURIMA TEST HOUSE STUDY
ED
UC
AT
IO N
AL
AN
SC
IE
NT
IFI C
PU
RP
OS
ES
ON
LY
18
RESULTS OF FORMALDEHYDE MEASUREMENT ( n = 0.3 h-1 inside the house)
FO
ED
UC
AT
IO N
AL
AN
SC
IE
NT
IFI C
PU
RP
OS
ES
ON
LY
Salthammer et al. (2010) Chemical Reviews Salthammer and Mentese (2008) Chemosphere
19
INDOOR FORMALDEHYDE: SUMMARY OF INTERNATIONAL STUDIES (in ppb)
FO
ED
UC
AT
IO N
25 17
AL
34
AN
20
17
D 23 10 56 SC IE 81 NT IF
20
28
27 31 72
72 111
15 25
IC
PU
RP
blue: median (50-P) green: geometric mean red: arithmetic mean
OS
ES
20
ON
LY
Data: from Salthammer et al. (2010) Chemical Reviews and WHO (2010)
20
500 MILLION PEOPLE LIVE IN THE 30 BIGGEST MEGACITIES
FO
ED
UC
AT
IO N
AL
AN
SC
IE
NT
IFI C
PU
RP
OS
ES
ON
LY
Picture: http://www.wikipedia.de
21
FORMALDEHYDE AS A SECONDARY POLLUTANT FROM OZONE REACTION
FO
ED
UC
AT
IO N
AL
AN
SC
IE
NT
IFI C
PU
RP
OS
ES
ON
LY
Criegee (1975) Angew. Chem. Int. Ed., 14, 745
22
FORMATION OF FORMALDEHYD BY ISOPRENE/OH/NO REACTION
FO
ED
UC
AT
IO N
AL
AN
SC
IE
NT
IFI C
PU
RP
OS
ES
ON
LY
Carter and Atkinson (1996) Int. J. Chem. Kin. 28, 497
23
CONCENTRATION OF NMHCS UND CARBONYLS IN BEIJING (SUMMER 2006)
FO
concentration in ambient air (g/m)
ED
UC
35 30 25 20 15 10 5 0
Formaldehyde
AT
IO N
AL
n-Hexane
AN
(VOC) = 264 g/m (N = 69)
SC
IE
n-Pentane Propane Ethene Acetylene Propene Isoprene

-Pinene
NT
IFI C
Toluene
m,p-Xylene Benzene
n-Undecane Ethan Methylcyclohexane
PU
Acetaldehyde
RP
Mesitylene
OS
Hexanal Benzaldehyde
Alkanes
Alkenes
arom. HC
Carbonyls
ES
compound class
Duan et al. (2008) Atmospheric Research 88, 25-35
ON
LY
24
FORMALDEHYDE: FROM INDOOR POLLUTANT TO OUTDOOR POLLUTANT?
FO
ED
UC
AT
IO N
AL
AN
SC
39
IE 39 NT IF
14
27 22
IC
113 54
PU
RP
OS
ES
ON
LY
25
FO
BIOFUEL COMBUSTION PRODUCES CARBONYL COMPOUNDS
ED
UC
AT
IO N
AL
AN
SC
IE
NT
The increased use of biofuel will increase the PU formaldehyde concenRP tration in ambient air. O
IFI C
SE
ON
LY
Kohse-Hinghaus et al. (2010) Angewandte Chemie Int. Ed.
26
FO
INTERNATIONAL INDOOR AIR FORMALDEHYDE GUIDELINES
ED 0.10
Korea (8h) UC Germany (confirmed 2006) AT Japan (0.5h) UK (0.5h) IO 0.08 NA short term 2010) China (1h) Australia Austria (8h) WHO (long and LA ND 0.06 SC IE NT 0.04 Canada (8h) Poland (24h) IFI C California (8h REL) Hong Kong (8h) P UR 0.02 PFrance (long term) OS ES California (chronic REL) 0.00 1977 1990 1995 2000 2005 2010 ON LY Year
Salthammer (2011) Chemosphere (modified)
Indoor Guideline (ppm)
27
DECREASING GUIDELINES AND INCREASING OUTDOOR VALUES OVERLAP
FO
ED 0.10 UC
0.09 0.08 0.07
AT
Decreasing indoor guidelines
IO N
AL
HCHO (ppm)
0.06 0.05 0.04 0.03 0.02 0.01 0.00
AN
SC
Correa et al. (2005), Rio de Janeiro - 113 ppb Khoder et al. (2000), Cairo - 39 ppb mean Duan et al. (2008), Beijing - 27 ppb during summer smog Bakeas et al. (2003), Athens - 14 ppb
IE
NT
IFI C
PU
RP
OS
ES
ON
LY
28
FO
FORMALDEHYDE ANALYTICS
ED acetyl acetone UC A
O O 2 O + HCHO + NH3
-3 H2O
Color Test
TIO
N H
DNPH
O2N
NA
NO2
NH-NH2 +
LA
R1 R2
R1 C=O -H2O O2N NH-N= NO2 R2
ND
TIF DNPH and acetyl acetone method (online or discontinuous) are IC suitable for the indoor related analysis of formaldehyde. PU ES 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
SC
IE
RP
OS
ON
LY
29
FO
false negative
false positive 5% color reaction (Y/N decision) with 95% reliability
ED
20 18 16 14 12 10 8 6 4 2 0 0
UC
5%
85%IO 15%
AT
NA
LA
ND
How high is the probability of the guideline value actually being exceeded when the detector tube shows this?
Density (%)
SC
Bayesian approach:
P( A / B)
IE
NT
50
100
150
200
250
HCHO (ppb)
1 IFI 1 0.77 0.05 0.85 P(B / A ) P( A ) 1 1 C 0.95 0.15 P(B PU ( A ) / A) P RP OS ES ON 300 350 LY
30
FO
MEANING OF A GUIDELINE FROM THE STATISTICAL POINT OF VIEW
R If a log-normal distribution is assumed for room air concentrations, it ED hardly makes sense from the statistical point of view to demand global U with complianceCA a guideline value. TIO
Density (%)
20 18 16 14 12 10 8 6 4 2 0 0 50 100 150 200 250
NA
LA
ND
log-normal fit curve
SC
IE
NT
IFI C
300
PU
350
HCHO (ppb)
RP
ON In principle all that the guideline value states is the percentage of LY exceedances which is acceptable!
OS
ES
31
FO
R the lower guideline always the better guideline ? IsE DU CA TIO NA LThe end justifies the means AN N. Machiavelli D SC IE NT IFI C PU R
Question 2: Does the benefit always justify the effort ?
Question 1:
PO
SE
ON
LY
32
FO
IS THE LOWER INDOOR GUIDELINE ALWAYS THE BETTER GUIDELINE ???
ED
high
UC
AT
IO N
Cost
AL
AN
Benefit
SC
IE
NT
IFI C
PU
SE Guideline
time
low
RP
ON
LY
33
FO
INDOOR AND OUTDOOR FORMALDEHYDE CONCENTRATION RANGES
ED
UC
AT
IO N
AL
AN
SC
IE
NT
IFI C
PU
RP
OS
ES
ON
LY
34
FO
SUMMARY AND CONCLUSION
R Industrial chemistry is needed to improve the quality of life for seven billion ED people on this planet. UC A ..formaldehyde is also an important indoor pollutant. LA C N
Formaldehyde is an important feedstock for building and consumer products, AT but.. IO In the indoor environment the formaldehyde concentrations are continuously ND decreasing (median or GM usually 20 40 ppb). S
IFI I reasonably doubt that indoor guidelines in theC range of 10 ppb are needed PU 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 polluON tant? LY
A long term a short term indoor guideline value of 0.08 ppm as derived by the IE WHO is scientifically sound and realistic.NT
35
FO
8th European Wood-Based Panel R ED Symposium 2012 U

Date: Location:
CA
TIO 10.-12.10.2012 NA Hannover, Maritim Airport Hotel LA ND SC IE NT IFI C PU
RP
OS
ES
ON
LY
36
FO
ED
UC
AT
Thank
IO N
AL for Your Attention YouAN D SC IE NT IFI C PU RP OS ES ON LY

A Critical Review of Indoor Formaldehyde Concentrations Guideline Values by Tunga Salthammer

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A Critical Review of Indoor Formaldehyde Concentrations Guideline Values by Tunga Salthammer

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Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

0.1 ppm = 100 ppb = 125 g/m

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

FORMALDEHYDE: PHYSICAL AND CHEMICAL PROPERTIES

CAS registry no.

50-00-0 HCHO, CH2O 30.03 g/mol -92 C -21 C

ANMelting point D SC Boiling point IE Dipole moment N

Henrys law constant log(Kow) b kOH kO3 kNO3

Salthammer et al. (2010) Chemical Reviews

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

INDUSTRIAL APPLICATION OF FORMALDEHYDE

Salthammer et al. (2010) Chemical Reviews

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

FORMALDEHYDE BASED RESINS FOR WOOD-BASED MATERIALS

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

N in HCHO T IFI indoor air C

combustion biogenic PUreactions RP OS

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

FORMALDEHYDE EMISSION FROM EXHALED BREATH GAS

1,6 1,4 1,2

HCHO (acac method, ppb)

1,0 0,8 0,6 0,4 0,2 0,0 0 10 20 30 40

Riess et al. (2010) Analytica Chimica Acta

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

BUILDING AND CONSUMER PRODUCTS MAY RELEASE FORMALDEHYDE

Salthammer et al. (2010) Chemical Reviews

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

UNEXPECTED FORMALDEHYDE EMISSION: PHOTOCATALYTIC WALL PAINT

Photocatalytic paint (P3) Formaldehyde Acetic aldehyde

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

FORMALDEHYDE TEST METHODS

Salthammer et al. (2010) Chemical Reviews

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

FORMALDEHYDE: RESULTS OF GERMAN ENVIRONMENTAL SURVEYS FO UNDER NORMAL LIVING CONDITIONS

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

FORMALDEHYDE: STEADY STATE CONCENTRATION IN GERMAN HOMES

Formaldehyde in private dwellings 367 data (1996-2006) lognormal fit curve

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

FORMALDEHYDE: MONTE-CARLO-SIMULATION (10000 runs)

log-normal fit curve

SERA = 30 g/(m h) (30 g/m = 25 ppb)

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

air exchange (h-1 )

Salthammer et al. (2010) Chemical Reviews

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

EMISSION AND EXPOSURE

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

WKI/EURIMA TEST HOUSE STUDY

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

RESULTS OF FORMALDEHYDE MEASUREMENT ( n = 0.3 h-1 inside the house)

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

INDOOR FORMALDEHYDE: SUMMARY OF INTERNATIONAL STUDIES (in ppb)

blue: median (50-P) green: geometric mean red: arithmetic mean

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

500 MILLION PEOPLE LIVE IN THE 30 BIGGEST MEGACITIES

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

FORMALDEHYDE AS A SECONDARY POLLUTANT FROM OZONE REACTION

Criegee (1975) Angew. Chem. Int. Ed., 14, 745

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

FORMATION OF FORMALDEHYD BY ISOPRENE/OH/NO REACTION

Carter and Atkinson (1996) Int. J. Chem. Kin. 28, 497

Formacare Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer

CONCENTRATION OF NMHCS UND CARBONYLS IN BEIJING (SUMMER 2006)

concentration in ambient air (g/m)

(VOC) = 264 g/m (N = 69)

n-Pentane Propane Ethene Acetylene Propene Isoprene