Skip to main content

LC–MS Analytical Method for Biomonitoring of Aliphatic and Aromatic Low-Molecular-Mass Aldehydes in Human Urine

Chromatographia volume 78, pages 203–209 (2015)Cite this article

Abstract

The aim of this study was to monitor aliphatic and aromatic low-molecular-mass aldehydes (LMMAs) in human urine to obtain a potential way to assess exposure. Aliquots of 12.5 mL of urine samples, diluted 1:1 with 4 mol L−1 hydrochloric acid, were aspirated into a Telos™ ENV μ-SPE column impregnated with 2,4-dinitrophenylhydrazine for the cleanup, derivatization and pre-concentration of the aldehydes. Determination was achieved by LC with a MS detector operating in the SIM mode. The method provided low LODs (90–300 ng L−1) with good precision (the intra- and inter-assay precision, expressed as RSD, ranged from 6.1 to 8.8 % and 7.1 to 9.1 %, respectively). Average recoveries from urine samples, which were spiked with the target analytes at levels of 2.5 and 10 μg L−1, ranged from 95 to 99 %. Only aliphatic LMMAs were found in urine samples from exposed researchers taken after handling these compounds. From the excretion kinetics of aldehydes (half-life times between 0.9 and 1.4 h), it was found that the dosage absorbed was eliminated within ~6 h after exposure.

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

USD 39.95

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

Fig. 1

References

  1. Richardson SD, Plewa MJ, Jazwierska ED, Schoeny R, DeMarini DM (2007) Occurrence, genotoxicity, and carcinogenicity of regulated and emerging disinfection by-products in drinking water: a review and roadmap for research. Mutat Res 636:178–262

    CAS  Article  Google Scholar 

  2. Seinfeld JH, Pandis SN (2006) Atmospheric chemistry and physics: from air pollution to climate change. Wiley, Hoboken

    Google Scholar 

  3. Rubio MA, Zamorano N, Lissi E, Rojas A, Gutiérrez L, Von Baer D (2006) Volatile carbonylic compounds in downtown Santiago, Chile. Chemosphere 62:1011–1020

    CAS  Article  Google Scholar 

  4. Richardson SD (2012) Environmental mass spectrometry: emerging contaminants and current issue. Anal Chem 84:747–778

    CAS  Article  Google Scholar 

  5. Serrano M, Silva M, Gallego M (2013) Development of an environment-friendly microextraction method for the determination of aliphatic and aromatic aldehydes in water. Anal Chim Acta 784:77–84

    CAS  Article  Google Scholar 

  6. Fernández-Molina JM, Silva M (2013) Trace determination of low-molecular-mass substituted benzaldehydes in treated water using micro solid-phase extraction followed by liquid chromatography–mass spectrometric detection. J Chromatogr A 1300:180–186

    Article  Google Scholar 

  7. Korchazhkina O, Exley C, Spencer SA (2003) Measurement by reversed-phase high-performance liquid chromatography of malondialdehyde in normal human urine following derivatisation with 2,4-dinitrophenylhydrazine. J Chromatogr B 794:353–362

    CAS  Article  Google Scholar 

  8. Chen F, Wang C, Zhang M, Zhang X, Liu Y, Ye J, Chu Q (2014) Sensitive determination of endogenous hexanal and heptanal in urine by hollow-fiber liquid-phase microextraction prior to capillary electrophoresis with amperometric detection. Talanta 119:83–89

    CAS  Article  Google Scholar 

  9. Xu H, Wang S, Zhang G, Huang S, Song D, Zhou Y, Long G (2011) A novel solid-phase microextraction method based on polymer monolith frit combining with high-performance liquid chromatography for determination of aldehydes in biological samples. Anal Chim Acta 690:86–93

    CAS  Article  Google Scholar 

  10. Zardari LA, Khuhawar MY, Laghari AJ (2009) Capillary GC analysis of glyoxal and methylglyoxal in the serum and urine of diabetic patients after use of 2,3-diamino-2,3-dimethylbutane as derivatizing reagent. Chromatographia 70:891–897

    CAS  Article  Google Scholar 

  11. Fiamegos YC, Stalikas CD (2008) Gas chromatographic determination of carbonyl compounds in biological and oil samples by headspace single-drop microextraction with in-drop derivatisation. Anal Chim Acta 609:175–183

    CAS  Article  Google Scholar 

  12. Konidari CN, Giannopoulos TS, Nanos CG, Stalikas CD (2005) Determination of plasma, urine, and bovine serum albumin low-molecular-weight carbonyl levels by capillary gas chromatography with electron-capture and mass-selective detection. Anal Biochem 338:62–70

    CAS  Article  Google Scholar 

  13. Montine TJ, Neely MD, Quinn JF, Beal MF, Markesbery WR, Roberts LJ, Morrow JD (2002) Serial review: causes and consequences of oxidative stress in Alzheimer’s disease. Free Radic Biol Med 33:620–626

    CAS  Article  Google Scholar 

  14. Yamada Y, Imai T, Ishizaki M, Honda R (2004) ALDH2 and CYP2E1 genotypes, urinary acetaldehyde excretion and the health consequences in moderate alcohol consumers. J Hum Genet 51:104–111

    Article  Google Scholar 

  15. Takamoto S, Sakura N, Namera A, Yashiki M (2004) Monitoring of urinary acrolein concentration in patients receiving cyclophosphamide and ifosphamide. J Chromatogr B 806:59–63

    CAS  Article  Google Scholar 

  16. Takeuchi A, Takigawa T, Abe M, Kawai T, Endo Y, Yasugi T, Endo G, Ogino K (2007) Determination of formaldehyde in urine by headspace gas chromatography. Bull Environ Contam Toxicol 79:1–4

    CAS  Article  Google Scholar 

  17. Baños CE, Silva M (2010) Liquid chromatography–tandem mass spectrometry for the determination of low-molecular mass aldehydes in human urine. J Chromatogr B 878:653–658

    Article  Google Scholar 

  18. Shah VP, Midha KK, Dighe S, McGilveray IJ, Skelly JP, Yacobi A, Layloff T, Viswanathan CT, Cook CE, McDowall RD, Pittman KA, Spector S (1992) Analytical methods validation: bioavailability, bioequivalence, and pharmacokinetic studies. Pharm Res 9:588–592

    Article  Google Scholar 

  19. Nowatzke W, Wool E (2007) Best practices during bioanalytical method validation for the characterization of assay reagents and the evaluation of analyte stability in assay standards, quality controls, and study samples. AAPS J 9:E117–E122

    CAS  Article  Google Scholar 

  20. Zwiener C, Glauner T, Frimmel FH (2002) Method optimization for the determination of carbonyl compounds in disinfected water by DNPH derivatization and LC–ESI–MS–MS. Anal Bioanal Chem 372:615–621

    CAS  Article  Google Scholar 

  21. Caro J, Gallego M (2007) Assessment of exposure of workers and swimmers to trihalomethanes in an indoor swimming pool. Environ Sci Technol 41:4793–4798

    CAS  Article  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the subsidy provided by the Spanish Inter-Ministerial Commission of Science and Technology of the Ministry of Education and Science under the CTQ2013-42701 and by the Junta de Andalucía under PO9-FQM-4732. European Regional Development Fund also provided additional funding. J.M. Fernández-Molina would also like to acknowledge the Junta de Andalucía for awarding him a predoctoral Grant.

Conflict of interest

The authors have declared no conflict of interest.

Author information

Authors and Affiliations

  1. Department of Analytical Chemistry, Marie-Curie Building (Annex), Rabanales Campus, University of Cordoba, 14071, Cordoba, Spain

    José María Fernández-Molina & Manuel Silva

Authors
  1. José María Fernández-Molina
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Manuel Silva
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Manuel Silva.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Fernández-Molina, J.M., Silva, M. LC–MS Analytical Method for Biomonitoring of Aliphatic and Aromatic Low-Molecular-Mass Aldehydes in Human Urine. Chromatographia 78, 203–209 (2015). https://doi.org/10.1007/s10337-014-2824-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10337-014-2824-4

Keywords

  • LC–MS
  • µ-SPE
  • 2,4-Dinitrophenylhydrazine
  • Urinary aldehydes
  • Excretion kinetics