Industrial Hygiene
Formaldehyde Analysis
Copyright © 2009 by DBS
Contents
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Colorimetric Analysis
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Acetylacetone Method
NIOSH 3500
Sampling
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Complaint area, non-complaint area and outside
Vapor phase extraction followed by analysis
Measurement
Methods
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Colorimetric
– Acetylacetone colorimetric method (Nash, 1953)
– NIOSH 3500
– Pararosaniline Method
HPLC
GC
See Schultz, M. and Salthammer, T (1999) for discussion of
methods
Measurement
Acetylacetone Colorimetric Method
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Acetylacetone colorimetric method (Nash, 1953)
– Hantzsch reagent (acetylacetone)
– 2M ammonium acetate, 0.05 M acetic acid, 0.02 M
acetylacetone
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See Shimadzu paper No. A262 for method
Measurement
Acetylacetone Colorimetric Method
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Stock HCHO solution = 37.7 % (m/m), ρ = 1.0108 g/mL
37.7 g HCHO
1g Sol.
1000 mg 1000 mL
x
x
x
 340,000 mg / L
100 g Sol.
1.0108 mL
g
L
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Require HCHO std. (1000 ppm), how much of the 37.7 % solution
should be taken to make a 100 mL solution of 1000 ppm HCHO?
C1V1  C2V 2
340,000 ppm x V1  100 mL x 1000 ppm
V1  0.294 mL
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Dilutions of 1000 ppm to make a 1,2, and 5 standard?
– 1:100 to make a 10 ppm std., then 1:10, 2:10 and 1:2
Measurement
Acetylacetone Colorimetric Method
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Measure out 2x 25 mL of absorption liquid (DI water) into 2
impingers (sample and equipment blank)
Pass air through one of the impingers at 1 L/min for 40 minutes
Perform the following to: a 5 mL reagent blank, a 5 mL 1000 ppm
Std., 5 mL of the air sample and the sample blank
– Add 5 mL acetlyacetone reagent and 5 mL DI water
– Heat for 30 mins at 40 °C
– Leave for color developemnt (30 mins)
Dilute the standard to 1, 2, and 5 ppm
Read standards and sample tubes at 412 nm, slit width 2.0 nm
Measurement
Acetylacetone Colorimetric Method
Shimadzu Paper No. A262
Measurement
Acetylacetone Colorimetric Method
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A
Measurement
NIOSH 3500: Chromotropic Acid Method
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UV-Vis
– NIOSH 3500 method uses chromotropic acid
– Detection limit: 0.5 µg per sample
Measurement
HPLC
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HPLC
Health Effects
Acute Exposure
Hess-Kosa, 2002
Summary
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Used in a wide variety of processes and products
Carcinogenic, irritant poses safety hazard
Max permissible exposure 2.0 – 0.1 mg/m3 very close to
demonstrated rodent carcinogenic dose of 5.6 mg/m3 and NOEL
of 2 mg/m3
Books
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Hess-Kosa, K. (2002) Indoor Air Quality. Lewis Publishers.
Leslie, G.B. and Lunau, F.W. (1992) Indoor Air Pollution: Problems
and Priorities. Cambridge University Press.
Turco, R.P. (2002) Earth Under Seige: From Air Pollution to Global
Change. Oxford University Press, London.
Turoski, V. (ed.) (1985) Formaldehyde: Analytical Chemistry and
Toxicology (Advances in Chemistry Series). ACS, Washington DC.
References
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Beasley, R.K., Hoffman, C.E., Rueppel, M.L., and Worley, J.W. (1980) Sampling of Formaldehyde in Air
with Coated Solid Sorbent and Determination by High Performance Liquid Chromatography. Analytical
Chemistry, Vol. 52, pp. 110-114.
Fregert, S., Dahlquist, I., and Gruvberger, B. (1984) A simple method for the detection of formaldehyde.
Contact Dermititis, Vol. 10, No. 3, pp. 132-134.
Gammage, R.B. and Gupta, K.C., “Formaldehyde”, in: Walsh, P.J., Dudney, C.S., and Copenhaver, E.D.,
eds. (1984) Indoor Air Quality. CRC Press, Boca Raton, Florida.
Gasparini, F., Weinert, P.L., Lima, L.S., Pezza, L., and Pezza, H.R. (2008) A simple and green analytical
method for the determination of formaldehyde. Journal of the Brazillian Chemical Society, Vol. 19, No. 8,
pp. 1531-1537.
Kleindienst, T.E. et al (1988) An intercomparison of formaldehyde measurement techniques at ambient
concentration. Atmospheric Environment, Vo. 22, No. 9, pp. 1931-1939.
Larson, A., Jentoft, N.A., and Greibrokk, T. (1992) Determination of ppb levels of formaldehyde in air.
Science of the Total Environment, Vol. 120, No. 3, pp. 261-269.
Lowe, D.C., Schmidt, U., Ehhalt, D.H., Frishkorn, C.G.B., and Nürnberg, H.W. (1981) Determination of
formaldehyde in clean air. Environmental Science and Technology, Vol. 15, No. 7, pp. 819-823.
Luks, E., Kiss, E. (1992) Formaldehyde determination by the colorimetric method with acetylacetone. Part
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Matthews, T.G., Hawthorne, A.R., Howell, T.C. et al (1982) Evaluation of selected monitoring methods for
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Matthews, T.G. and Howell, T.C. (1981) Visual colorimetric formaldehyde screening analysis for indoor
air. Journal of the Air Pollution Control Association, Vol. 31, No. 11, pp. 1181-1184.
References
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Miksch, R.R., Anthon, D.W., Fanning, L.Z., Hollowell, C.D., Revzan, K., and Glanville, J.
(1981) Modified Pararosaniline Method for the Determination of Formaldehyde in Air.
Analytical Chemistry, Vol. 53, pp. 2118-2123.
Monsen, R.M. and Stock, T.H. (1986) A comparison of formaldehyde monitoring methods
for the residential environment. Journal of Environmental Health, Vol. 49, No. 2, pp. 72-75.
Murai, K., Okano, M., Kuramitz, H., Hata, N., Kawakami, T., and Taguchi, S. (2008)
Investigation of formaldehyde pollution of tap water and rain water using a novel visual
colorimetry. Water Science and Technology, Vol. 58, No. 5, pp. 1055-1060.
Nash, T. (1952) Colorimetric Determination of Formaldehyde under Mild Conditions.
Nature, Vol. 170, No. 4336, pp. 976.
Nash, T. (1953) The Colorimetric Estimation of Formaldehyde by Means of the Hantzsch
Reaction. Biochemistry, Vol. 55, p. 416-421.
Peatreas, M., Twist, S., Pon, D., and Miles, I. (1984) Evaluation of Two Methods for
Measuring Formaldehyde at ppb Levels. Proceedings, Annual Meeting – Air Pollution
Control Association, Vol. 6, 10p.
Trebig, G., Schaller, K.-H., Beyer, B., Muller, J., and Valentin, H. (1989) Formaldehyde
exposure at various workplaces. Science of the Total Environment, Vol. 79, No. 2, pp.
191-195.
West, P.W. and Sen, B. (1956) Spectrophotometric determination of traces of
formaldehyde. Fresenius’ Zeitschrift fur Analytische Chemie, Vol. 153, No. 3, pp. 177-183.