Industrial Hygiene

Formaldehyde Analysis

Copyright © 2009 by DBS

Contents

• Colorimetric Analysis– Acetylacetone Method

– NIOSH 3500

Sampling

• Complaint area, non-complaint area and outside

• Vapor phase extraction followed by analysis

MeasurementMethods

• Colorimetric

– Acetylacetone colorimetric method (Nash, 1953)

– NIOSH 3500

– Pararosaniline Method

• HPLC

• GC

• See Schultz, M. and Salthammer, T (1999) for discussion of methods

MeasurementAcetylacetone Colorimetric Method

• Acetylacetone colorimetric method (Nash, 1953)

– Hantzsch reagent (acetylacetone)

– 2M ammonium acetate, 0.05 M acetic acid, 0.02 M acetylacetone

• See Shimadzu paper No. A262 for method

MeasurementAcetylacetone Colorimetric Method

• Stock HCHO solution = 37.7 % (m/m), ρ = 1.0108 g/mL

• 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?

• 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

LmgL

mLx

g

mgx

mL

Solgx

Solg

HCHOg/000,340

10001000

0108.1

.1

.100

7.37

mLV

ppmxmLVxppm

VCVC

294.0

1000100000,340

1

1

211 2

MeasurementAcetylacetone Colorimetric Method

• 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

MeasurementAcetylacetone Colorimetric Method

Shimadzu Paper No. A262

MeasurementAcetylacetone Colorimetric Method

• A

Measurement NIOSH 3500: Chromotropic Acid Method

• UV-Vis

– NIOSH 3500 method uses chromotropic acid

– Detection limit: 0.5 µg per sample

Measurement HPLC

• HPLC

Health EffectsAcute Exposure

Hess-Kosa, 2002

Summary

• 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

• 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• 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 I. Formaldehyde determination in certain cosmetic products. Roczniki Panstwowego Zakladu Higieny, Vol. 43, No., 3-4, pp. 289-293.

• Matthews, T.G., Hawthorne, A.R., Howell, T.C. et al (1982) Evaluation of selected monitoring methods for formaldehyde in domestic environments. Environment International. Vol. 8, No. 1-6, p. 143-151.

• 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

• 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.