Skip to main content
SpringerLink
Log in

GDME-based methodology for the determination of free formaldehyde in cosmetics and hygiene products containing formaldehyde releasers

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Formaldehyde is often applied in the industrial production of different products, such as textiles, insulation materials, or cosmetics, due to its preservative and disinfectant properties. However, formaldehyde is classified by the International Agency for Research on Cancer as carcinogenic, and there are numerous studies about the pernicious health effects that frequent exposure to formaldehyde can pose to human health. In the cosmetic industry, compounds called formaldehyde releasers are added during production, with the intent of releasing small amounts of formaldehyde over time. Although there are many methods available for the determination of formaldehyde, they are usually not suitable for the determination of free formaldehyde in cosmetics with formaldehyde releasers in their composition, as they can promote the accelerated release of formaldehyde. In this work, the gas-diffusion microextraction (GDME) technique was used for the extraction of formaldehyde from cosmetic and personal hygiene products. Acetylacetone was used as the derivatization reagent which was later used for the spectrophotometric determination of formaldehyde. The developed methodology exhibits limits of detection (1.98 mg kg−1) and quantification (6.60 mg kg−1) perfectly adequate for the determination of formaldehyde in these samples. Formaldehyde values between 6.9 ± 0.3 and 365 ± 15 mg kg−1 were found in samples containing the formaldehyde releasers DMDM hydantoin, Diazolidinyl urea, and Bronopol. Furthermore, mass spectrometry studies were performed in order to unbiasedly ensure the presence of formaldehyde in every extract. GDME proved to be an economical, simple, and robust alternative for the extraction of free formaldehyde in personal hygiene and cosmetic samples.

ᅟ

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Winkelman JGM, Voorwinde OK, Ottens M, Beenackers AACM, Janssen LPBM. Kinetics and chemical equilibrium of the hydration of formaldehyde. Chem Eng Sci. 2002;57:4067–76.

    Article  CAS  Google Scholar 

  2. Boyer IJ, Heldreth B, Bergfeld WF, Belsito DV, Hill RA, Klaassen CD, et al. Amended safety assessment of formaldehyde and methylene glycol as used in cosmetics. Int J Toxicol. 2013;32:5S–32S.

    Article  CAS  PubMed  Google Scholar 

  3. Salthammer T, Mentese S, Marutzky R. Formaldehyde in the indoor environment. Chem Rev. 2010;110:2536–72.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  4. Lefebvre MA, Meuling WJA, Engel R, Coroama MC, Renner G, Pape W, et al. Consumer inhalation exposure to formaldehyde from the use of personal care products/cosmetics. Regul Toxicol Pharmacol. 2012;63:171–6.

    Article  CAS  PubMed  Google Scholar 

  5. Lavilla I, Cabaleiro N, Pena F, de la Calle I, Bendicho C. Ultrasound-assisted emulsification microextraction with simultaneous derivatization coupled to fibre optics-based cuvetteless UV-vis micro-spectrophotometry for formaldehyde determination in cosmetic samples. Anal Chim Acta. 2010;674:59–63.

    Article  CAS  PubMed  Google Scholar 

  6. Rivero RT, Topiwala V. Quantitative determination of formaldehyde in cosmetics using a combined solid-phase microextraction-isotope dilution mass spectrometry method. J Chromatogr A. 2004;1029:217–22.

    Article  CAS  PubMed  Google Scholar 

  7. Wolf R, Orion E, Ruocco E, Baroni A, Ruocco V. Contact dermatitis: facts and controversies. Clin Dermatol. 2013;31:467–78.

    Article  PubMed  Google Scholar 

  8. Lundov MD, Johansen JD, Carlsen BC, Engkilde K, Menné T, Thyssen JP. Formaldehyde exposure and patterns of concomitant contact allergy to formaldehyde and formaldehyde-releasers. Contact Dermatitis. 2010;63:31–6.

    Article  CAS  PubMed  Google Scholar 

  9. Lv C, Hou J, Xie W, Cheng H. Investigation on formaldehyde release from preservatives in cosmetics. Int J Cosmetic Sci. 2015;37:474–8.

    Article  CAS  Google Scholar 

  10. Malinauskiene L, Blaziene A, Chomiciene A, Isaksson M. Formaldehyde may be found in cosmetic products even when unlabelled. Open Medicine (Poland). 2015;10:323–8.

    Google Scholar 

  11. De Groot AC, Flyvholm MA, Lensen G, Menné T, Coenraads PJ. Formaldehyde-releasers: relationship to formaldehyde contact allergy. Contact allergy to formaldehyde and inventory of formaldehyde-releasers. Contact Dermatitis. 2009;61:63–85.

    Article  PubMed  Google Scholar 

  12. Lehmann SV, Hoeck U, Breinholdt J, Olsen CE, Kreilgaard B. Characterization and chemistry of imidazolidinyl urea and diazolidinyl urea. Contact Dermatitis. 2006;54:50–8.

    Article  CAS  PubMed  Google Scholar 

  13. Kajimura K, Tagami T, Yamamoto T, Iwagami S. The release of formaldehyde upon decomposition of 2-bromo-2-nitropropan-1, 3-diol (bronopol). J Health Sci. 2008;54:488–92.

    Article  CAS  Google Scholar 

  14. De Groot AC, Van Joost T, Bos JD, Van der Meeren HLM, Weyland JW. Patch test reactivity to DMDM hydantoin. Relationship to formaldehyde allergy. Contact Dermatitis. 1988;18:197–201.

    Article  PubMed  Google Scholar 

  15. Jackson EM. Formalehyde in personal care products. Skin Pharmacol Physiol. 2012;25:236–40.

    Article  CAS  PubMed  Google Scholar 

  16. Karlberg AT, Skare L, Lindberg I, Nyhammar E. A method for quantification of formaldehyde in the presence of formaldehyde donors in skin-care products. Contact Dermatitis. 1998;38:20–8.

    Article  CAS  PubMed  Google Scholar 

  17. Commission Directive of 4th April 1990 (90/207 EEC) (IV). Identification and determination of free formaldehyde. Official Journal of European Communities no. L108, 28/04/90 pp. 92–101. 1990.

  18. Lv C, Sun J, Cheng H. Determination of formaldehyde residue in cosmetics by short-column high performance liquid chromatography with mass spectrometric confirmation. Anal Methods. 2015;7:1630–4.

    Article  CAS  Google Scholar 

  19. Doi T, Kajimura K, Taguchi S. Survey of formaldehyde (FA) concentration in cosmetics containing FA-donor preservatives. J Health Sci. 2010;56:116–22.

    Article  CAS  Google Scholar 

  20. European Union - Second Commission Directive on the approximation of the laws of the Member States relating to methods of analysis necessary for checking the composition of cosmetic products. Off. J. Eur. Commun. 1982 No. L185, pp. 1–28.

  21. Miralles P, Chisvert A, Alonso MJ, Hernandorena S, Salvador A. Determination of free formaldehyde in cosmetics containing formaldehyde-releasing preservatives by reversed-phase dispersive liquid–liquid microextraction and liquid chromatography with post-column derivatization. J Chromatogr A. 2018;1543:34–9.

    Article  CAS  PubMed  Google Scholar 

  22. Ramos RM, Pacheco JG, Gonçalves LM, Valente IM, Rodrigues JA, Barros AA. Determination of free and total diacetyl in wine by HPLC–UV using gas-diffusion microextraction and pre-column derivatization. Food Control. 2012;24:220–4.

    Article  CAS  Google Scholar 

  23. Ferreira RC, Ramos RM, Goncalves LM, Almeida PJ, Rodrigues JA. Application of gas-diffusion microextraction to solid samples using the chromatographic determination of α-diketones in bread as a case study. Analyst. 2015;140:3648–53.

    Article  CAS  PubMed  Google Scholar 

  24. Ramos RM, Gonçalves LM, Vyskočil V, Rodrigues JA. Free sulphite determination in wine using screen-printed carbon electrodes with prior gas-diffusion microextraction. Electrochem Commun. 2016;63:52–5.

    Article  CAS  Google Scholar 

  25. Brandão PF, Ramos RM, Almeida PJ, Rodrigues JA. Determination of carbonyl compounds in Cork agglomerates by GDME-HPLC-UV: identification of the extracted compounds by HPLC-MS/MS. J Agric Food Chem. 2017;65:1037–42.

    Article  CAS  PubMed  Google Scholar 

  26. Brandão PF, Ramos RM, Valente IM, Almeida PJ, Carro AM, Lorenzo RA et al. Gas-diffusion microextraction coupled with spectrophotometry for the determination of formaldehyde in cork agglomerates. Anal Bioanal Chem 2017:1–8.

  27. Ramos RM, Brandão PF, Gonçalves LM, Vyskočil V, Rodrigues JA. Electrochemical sensing of total sulphites in beer using non-modified screen-printed carbon electrodes. J Inst Brew. 2017;123:45–8.

    Article  CAS  Google Scholar 

  28. Pacheco JG, Valente IM, Gonçalves LM, Rodrigues JA, Barros AA. Gas-diffusion microextraction. J Sep Sci. 2010;33:3207–12.

    Article  CAS  PubMed  Google Scholar 

  29. Valente IM, Oliveira HM, Vaz CD, Ramos RM, Fonseca AJM, Cabrita ARJ, et al. Determination of ammonia nitrogen in solid and liquid high-complex matrices using one-step gas-diffusion microextraction and fluorimetric detection. Talanta. 2017;167:747–53.

    Article  CAS  PubMed  Google Scholar 

  30. Ramos RM, Gonçalves LM, Vyskočil V, Rodrigues JA. Voltammetric determination of trace amounts of diacetyl at a mercury meniscus modified silver solid amalgam electrode following gas-diffusion microextraction. Talanta. 2017;169:203–8.

    Article  CAS  PubMed  Google Scholar 

  31. Backe WJ. A novel mass spectrometric method for formaldehyde in children's personal-care products and water via derivatization with acetylacetone. Rapid Commun Mass Spectrom. 2017;31:1047–56.

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

The authors would like to thank Dr. Zélia Azevedo for the HPLC-MS/MS analyses.

Funding

This work received financial support from the European Union (FEDER funds POCI/01/0145/FEDER/007265) and from FCT/MEC through national funds and co-financed by FEDER (UID/QUI/50006/2013; NORTE-01-0145-FEDER-00011) under Partnership Agreement PT2020, which includes a studentship to PFB and RMR.

Author information

Authors and Affiliations

  1. REQUIMTE/LAQV—Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, no. 687, 4169-007, Porto, Portugal

    Pedro Francisco Brandão, Rui Miguel Ramos & José António Rodrigues

Authors
  1. Pedro Francisco Brandão
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rui Miguel Ramos
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. José António Rodrigues
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Rui Miguel Ramos.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Brandão, P.F., Ramos, R.M. & Rodrigues, J.A. GDME-based methodology for the determination of free formaldehyde in cosmetics and hygiene products containing formaldehyde releasers. Anal Bioanal Chem 410, 6873–6880 (2018). https://doi.org/10.1007/s00216-018-1287-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-018-1287-0

Keywords

Search

Navigation