Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer FO R 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 1 Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 2 FO TOPICS R ED UC Formaldehyde basics AT IO Formaldehyde application NA FormaldehydeLindoor AN concentrations D Formaldehyde tropospheric SC chemistry IE NT From indoor towards outdoor? IFI C Formaldehyde air quality guidelines PU R Summary and Conclusion PO 0.1 ppm = 100 ppb = 125 µg/m³ SE S ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 3 FORMALDEHYDE: PHYSICAL AND CHEMICAL PROPERTIES FO R ED UC Structure AT IO N 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 TIF 2.33 D IC soluble in water, ethanol, ether, acetone PU 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 RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 4 INDUSTRIAL APPLICATION OF FORMALDEHYDE FO R ED UC AT IO N AL AN D Salthammer et al. (2010) Chemical Reviews SC IE NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 5 FORMALDEHYDE BASED RESINS FOR WOOD-BASED MATERIALS FO R ED UC AT urea-formaldehyde-resin IO N AL AN melamine-formaldehyde-resin phenol-formaldehyde-resin D SC IE NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 6 FORMALDEHYDE SOURCES FO R ED HCHO UC Processing AT Product IO N AL AN free HCHO D outdoor air Temperature Humidity SC IE NTin HCHO I indoor air FIC Ozone VOCs Product Salthammer et al. (2010) Chemical Reviews back reaction combustion biogenic PUreactions RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 8 FORMALDEHYDE EMISSION FROM EXHALED BREATH GAS R 1,6 ED UC AT IO N AL 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 IE NT HCHO (acac method, ppb) consumption of alcohol 1,4 SC 40 5 4 3 2 IFI C smoking 2 cigarettes FO cigarette smoking PU RP 1 0 0 10 OS ES 20 time (min) 30 ON LY 40 Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 9 BUILDING AND CONSUMER PRODUCTS MAY RELEASE FORMALDEHYDE FO R ED U 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…….. Salthammer et al. (2010) Chemical Reviews ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 10 UNEXPECTED FORMALDEHYDE EMISSION: PHOTOCATALYTIC WALL PAINT FO R ED110 UC 100 A Concentration (µg/m3) 90 80 70 Photocatalytic paint (P3) Formaldehyde Acetic aldehyde TIO NA 60 LA ND 50 light off SC IE NT light on 40 IFI C 30 20 PU 10 0 40 60 80 100 120 time (h) Salthammer and Fuhrmann (2007) ES&T 140 RP OS 160 ES 180 ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 11 FORMALDEHYDE TEST METHODS FO R ED UC AT 48 m³ chamber IO N AL AN D 1 m³ chamber Salthammer et al. (2010) Chemical Reviews SC IE NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 12 FORMALDEHYDE: RESULTS OF GERMAN ENVIRONMENTAL SURVEYS FO NORMAL LIVING CONDITIONS UNDER ED U300 CA German Environmental Survey TIO 1985-86 (N = 329) 250 NA 2003-06 (N = 586) LA ND 200 SC IE 150 NT IFI 100 C formaldehyde (µg m -3 ) R 50 PU RP OS 0 P-10 P-50 P-90 P-95 P-98 Parameter Salthammer et al. (2010) Chemical Reviews GM AM Max ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 13 FORMALDEHYDE: STEADY STATE CONCENTRATION IN GERMAN HOMES FO R ED 25 UC 20 AT IO N AL N (%) 15 Formaldehyde in private dwellings 367 data (1996-2006) lognormal fit curve AN D SC 10 IE NT IFI C 5 0 0.05 0.10 0.15 HCHO (ppm) Salthammer et al. (2010) Chemical Reviews PU 0.20 RP OS ES 0.25 ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 14 FORMALDEHYDE: MONTE-CARLO-SIMULATION (10000 runs) FO R 20 ED 18 U CA 16 Density (%) 14 TIO 12 log-normal fit curve NA LA 10 ND SER A L Cs n SC IE SERA = 30 µg/(m² h) (30 µg/m³ = 25 ppb) 8 NT IFI C L = 0.5 – 1.5 m²/m³ (uniform distribution) 6 n = 0.05 – 0.95 h-1 (uniform distribution) 4 2 0 0 50 100 150 200 HCHO (ppb) Salthammer (2011) Chemosphere 250 PU RP 300 OS ES 350 ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 15 FORMALDEHYDE AND AIR EXCHANGE F(extracted from the 1996-2006 steady state concentrations) ED UC 0.20 AT 0.15 IO N HCHO (ppm) OR 0.10 0.05 AL AN D 0.00 1.0 1996 SC IE 2001 air exchange (h-1 ) 0.8 0.6 NT 2006 IFI C PU 0.4 0.2 0.0 1996 Salthammer et al. (2010) Chemical Reviews 2001 2006 RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 16 EMISSION AND EXPOSURE FO R ED UC AT Emission source Emission IO N Living behavior AL AN D SC IE NT Indoor Air pollution Exposure IFI C PU RP Climatic conditions OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 17 WKI/EURIMA TEST HOUSE STUDY FO R ED UC AT IO N AL AN D SC IE NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 18 RESULTS OF FORMALDEHYDE MEASUREMENT ( n = 0.3 h-1 inside the house) FO R ED UC AT IO N AL AN D SC Salthammer et al. (2010) Chemical Reviews Salthammer and Mentese (2008) Chemosphere IE NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 19 INDOOR FORMALDEHYDE: SUMMARY OF INTERNATIONAL STUDIES (in ppb) FO R ED UC AT IO N 25 17 17 AL 34 AN 20 28 D 23 10 56 SC IE 81 NT IF 20 27 PU blue: median (50-P) green: geometric mean red: arithmetic mean Data: from Salthammer et al. (2010) Chemical Reviews and WHO (2010) 111 72 31 IC 72 RP OS 15 25 20 ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 20 500 MILLION PEOPLE LIVE IN THE 30 BIGGEST MEGACITIES FO R ED UC AT IO N AL Picture: http://www.wikipedia.de AN D SC IE NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 21 FORMALDEHYDE AS A SECONDARY POLLUTANT FROM OZONE REACTION FO R ED UC AT IO N AL AN D SC Criegee (1975) Angew. Chem. Int. Ed., 14, 745 IE NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 22 FORMATION OF FORMALDEHYD BY ISOPRENE/OH/NO REACTION FO R ED UC AT IO N AL AN D SC IE Carter and Atkinson (1996) Int. J. Chem. Kin. 28, 497 NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 23 CONCENTRATION OF NMHCS UND CARBONYLS IN BEIJING (SUMMER 2006) R ED concentration in ambient air (µg/m³) FO UC Formaldehyde 35 AT 30 25 20 IO N AL n-Hexane AN (VOC) = 264 µg/m³ (N = 69) D 15 10 5 0 SC IE n-Pentane Propane n-Undecane Ethan Methylcyclohexane Alkanes Ethene Acetylene Propene Isoprene -Pinene Alkenes NT IFI C Toluene Mesitylene arom. HC compound class Duan et al. (2008) Atmospheric Research 88, 25-35 Acetaldehyde PU m,p-Xylene Benzene RP OS Hexanal Benzaldehyde Carbonyls ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 24 FORMALDEHYDE: FROM INDOOR POLLUTANT TO OUTDOOR POLLUTANT? FO R ED UC AT IO N AL AN 39 D SC 14 IE 39 NT IF 27 22 IC 113 54 PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 25 BIOFUEL COMBUSTION PRODUCES CARBONYL COMPOUNDS FO R ED UC AT IO N AL AN D SC IE NT IFI C The increased use of biofuel will increase the Pformaldehyde concenUR PO tration in ambient air. SE S Kohse-Höinghaus et al. (2010) Angewandte Chemie Int. Ed. ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer INTERNATIONAL INDOOR AIR FORMALDEHYDE GUIDELINES FO Indoor Guideline (ppm) R E0.10 D Korea (8h) UC Germany (confirmed 2006) AT Japan (0.5h) UK (0.5h) I ON 0.08 Austria (8h) ALshort term 2010) China (1h) Australia WHO (long and AN 0.06 D SC IE NT 0.04 Canada (8h) Poland (24h) IFI C California (8h REL) Hong Kong (8h) P UR 0.02 PFrance OS (long term) ES California (chronic REL) 0.00 1977 1990 1995 2000 2005 2010 ON LY Year Salthammer (2011) Chemosphere (modified) 26 Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 27 DECREASING GUIDELINES AND INCREASING OUTDOOR VALUES OVERLAP FO R E0.10 DU C 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 IO N AL AN D SC IE NT IFI C Correa et al. (2005), Rio de Janeiro - 113 ppb Khoder et al. (2000), Cairo - 39 ppb mean PU RP Duan et al. (2008), Beijing - 27 ppb during summer smog Bakeas et al. (2003), Athens - 14 ppb OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 28 FORMALDEHYDE ANALYTICS FO R ED acetyl acetone UC A DNPH O O 2 TIO O2N Color Test O O + HCHO + NH3 -3 H2O N H NA LA NH-NH2 + NO2 R1 R1 C=O ND R2 -H2O O2N NH-N= SC NO2 R2 IE N TIF DNPH and acetyl acetone method (online or discontinuous) are IC suitable for the indoor related analysis of formaldehyde. PU RP OS 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 ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer FO R false negative ED false positive 5% AT 85%IO 15% 18 NA LA 16 14 Density (%) color reaction (Y/N decision) with 95% reliability 5% UC 20 12 ND How high is the probability of the guideline value actually being exceeded when the detector tube shows this? SC IE 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 ) RP OS ES ON 300 350 LY P( A / B) 8 6 4 2 0 0 50 29 100 150 200 HCHO (ppb) Salthammer (2011) Chemosphere 250 Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 30 MEANING OF A GUIDELINE FROM THE STATISTICAL POINT OF VIEW FO 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 LA 18 16 ND Density (%) 14 12 10 log-normal fit curve SC IE 8 6 NT IFI C 4 2 0 0 50 100 150 200 HCHO (ppb) 250 300 PU 350 RP OS ES ON of In principle all that the guideline value states is the percentage LY exceedances which is acceptable! Salthammer (2011) Chemosphere Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer FO 31 Question 1: RIs the lower guideline always the better guideline ? ED UC AT IO NA L“The ANend justifies the means” N. Machiavelli D SC IE NT IFI C PU R Question 2: Does the benefit always justify the effort ? PO SE S ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 32 IS THE LOWER INDOOR GUIDELINE ALWAYS THE BETTER GUIDELINE ??? FO ED UC AT Cost IO N AL AN Benefit D SC IE NT time Salthammer (2011) Chemosphere IFI C PU RP O SE Guideline low high R S ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 33 INDOOR AND OUTDOOR FORMALDEHYDE CONCENTRATION RANGES FO R ED UC AT IO N AL AN D Salthammer et al. (2010) Chemical Reviews SC IE NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer SUMMARY AND CONCLUSION FO R Industrial chemistry is needed to improve the quality of life for seven billion E peopleDon this planet. UC Formaldehyde ATis an important feedstock for building and consumer products, but….. IO N A an important indoor pollutant. …..formaldehyde is also LA In the indoor environment the NDformaldehyde concentrations are continuously decreasing (median or GM usually S20 – 40 ppb). C 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 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 ONpollutant? LY 34 Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer 35 8th European Wood-Based Panel R ED Symposium 2012 U FO • • CA Date: Location: TIO 10.-12.10.2012 NHannover, Maritim Airport Hotel AL AN D SC IE NT IFI C PU RP OS ES ON LY Formacare – Formaldehyde Science Conference, Madrid, 19.-20.04.2012 - Salthammer FO R ED UC AT Thank IO N A L A for Your Attention You ND SC IE NT IFI C PU RP OS ES ON LY 36
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