Environmental Chemistry Letters

, Volume 17, Issue 3, pp 1405–1411 | Cite as

Fast determination of total aldehydes in rainwaters in the presence of interfering compounds

  • Sergii SukharevEmail author
  • Ruslan Mariychuk
  • Mykhajlo Onysko
  • Oksana Sukhareva
  • Svitlana Delegan-Kokaiko
Original Paper


C1–C5 aldehydes are toxic substances formed by chemical transformation of organic compounds into the atmosphere. Actual methods used to analyze aldehydes in environmental samples are usually slow and complex, whereas there is a need for rapid and frequent monitoring. Here, a simple, fast method for the spectrophotometric determination of the total content of aldehydes in waters has been developed. The method is based on the spectrophotometric determination at 478 nm of hydrazones in an alkaline medium, generating the hydrazon-α-oxiazinic tautomeric forms, which are formed by condensation of aldehydes and 3,5-dinitrobenzhydrazide (3,5-DHBA). We optimized the conditions of the condensation reaction, e.g., 0.05–1.0 mol L−1 H2SO4, heating at 95 °C for 10 min, and the procedure of the spectrophotometric determination of the total aldehyde content at pH higher than 11 and λmax of 478 nm. Those conditions allow the determination of the total aldehyde content in the presence of various interferences, e.g., most ketones including acetone, 2000-fold of anions: HCO3, CH3COO, SO42−, Cl, F and cations: Li+, Na+, K+, Mg2+, Ca2+, Sr2+. The calibration curve was linear in the range of 0.087–13.5 mg L−1 for aldehydes, with R2 of 0.99; the limit of detection was 27 μg L−1 (0.9 μmol L−1) and the limit of determination was 87 μg L−1 (3.2 μmol L−1) in terms of formaldehyde. The suggested procedure was successfully applied for the determination of the total aldehyde content in rainwaters and model mixtures with recovery of 97.8–102.7%. The accuracy of the procedure was confirmed by an analysis with a reference method.


Carbonyl compounds Spectrophotometric determination Rainwaters Reaction of condensation Hydrazones 



This work has been supported by the National Scholarship Program for the Supports of Mobility of University Students, PhD Students, University Teachers, Researchers and Artist of the Slovak Republic, SAIA.


  1. Afkhami A, Rezaei M (1999) Sensitive spectrophotometric determination of formaldehyde by inhibition of the malachite green-sulfite reaction. Microchem J 63:243–249. CrossRefGoogle Scholar
  2. Balla D, Papageorgiou A, Voutsa D (2014) Carbonyl compounds and dissolved organic carbon in rainwater of an urban atmosphere. Environ Sci Pollut Res Int 20:12062–12073. CrossRefGoogle Scholar
  3. Banos C-E, Silva M (2009) In situ continuous derivatization/pre-concentration of carbonyl compounds with 2,4-dinitrophenylhydrazine in aqueous samples by solid-phase extraction Application to liquid chromatography determination of aldehydes. Talanta 77:1597–1602. CrossRefGoogle Scholar
  4. Büldt A, Karst U (1997) 1-Methyl-1-(2,4-dinitrophenyl)hydrazine as a new reagent for the HPLC determination of aldehydes. Anal Chem 69:3617–3622. CrossRefGoogle Scholar
  5. Cancho B, Ventura F, Galceran MT (2001) Determination of aldehydes in drinking water using pentafluorobenzylhydroxylamine derivatization and solid-phase microextraction. J Chromatogr A 943:1–13. CrossRefGoogle Scholar
  6. Chundak SY, Sukharev SN (1997) Salicylidene hydrazones of carboxylic acids as reagents for the solvent-extraction-photometric determination of aluminum as ion pairs with cyanine dyes. J Anal Chem 52:542–547Google Scholar
  7. Conolly RB, Kimbell JS, Janszen D, Schlosser PM, Kalisak D, Preston J, Miller FJ (2003) Biologically motivated computational modeling of formaldehyde carcinogenicity in the F344 rat. Toxicol Sci 75:432–447. CrossRefGoogle Scholar
  8. Dasgupta PK, Zhang G, Schulze S, Marx JN (1994) Measurement of carbonyl compounds as the 2,4-dinitrophenylhydrazonate anion. Reaction mechanism and an automated measurement system. Anal Chem 66:1965–1970. CrossRefGoogle Scholar
  9. de Oliveira FS, Leite BCO, de Andrade MVAS, Korn M (2005) Determination of total aldehydes in fuel ethanol by MBTH method—sequential injection analysis. J Braz Chem Soc 16:87–92. CrossRefGoogle Scholar
  10. Deng C, Zhang X (2004) A simple, rapid and sensitive method for determination of aldehydes in human blood by gas chromatography/mass spectrometry and solid-phase microextraction with on-fiber derivatization. Rapid Commun Mass Spectrom 18:1715–1720. CrossRefGoogle Scholar
  11. Dossi N, Susmel S, Toniolo R, Pizzariello A, Bontempelli G (2009) Application of microchip electrophoresis with electrochemical detection to environmental aldehyde monitoring. Electrophoresis 30:3465–3471. CrossRefGoogle Scholar
  12. Endo Y, Li CM, Tagiri-Endo M, Fujimoto K (2001) A modified method for the estimation of total carbonyl compounds in heated and frying oils using 2-propanol as a solvent. JAOCS 78:1021–1024. CrossRefGoogle Scholar
  13. Endo Y, Tominaga M, Tagiri-Endo M, Kumozaki K, Kouzui H, Shiramasa H, Miyakoshi K (2003) A modified method to estimate total carbonyl compounds in frying oils using 1-butanol as a solvent. J Oleo Sci 52:353–358. CrossRefGoogle Scholar
  14. ISO 16000-3:2011. Indoor air. Part 3: Determination of formaldehyde and other carbonyl compounds in indoor air and test chamber air. Active sampling methodGoogle Scholar
  15. Kanwal S, Fu X, Su X (2011) Highly sensitive flow-injection chemiluminescence detection of carbonyl compounds in wine samples. Anal Lett 44:4–11. CrossRefGoogle Scholar
  16. Katritzky AR, Huang L, Chahar M, Sakhuja R, Hall CD (2012) The chemistry of N-hydroxyamidoximes, N-aminoamidoximes, and hydrazidines. Chem Rev 112:1633–1649. CrossRefGoogle Scholar
  17. Kuznetsov NV, Komarova LI, Safronova LP (1963) New reagent for the carbonyl group: 3,5-dinitrobenzoic hydrazide. Bull Acad Sci USSR Div Chem Sci 12:671–672. CrossRefGoogle Scholar
  18. Li Q, Sritharathikhun P, Motomizu S (2007) Development of novel reagent for Hantzsch reaction for the determination of formaldehyde by spectrophotometry and fluorometry. Anal Sci 23:413–417. CrossRefGoogle Scholar
  19. Lin Y-L, Wang P-Y, Hsieh L-L, Ku K-H, Yeh Y-T, Wu C-H (2009) Determination of linear aliphatic aldehydes in heavy metal containing waters by high-performance liquid chromatography using 2,4-dinitrophenylhydrazine derivatization. J Chromatogr A 1216:6377–6381. CrossRefGoogle Scholar
  20. Meek ME (2004) Toxicological highlight. Biologically motivated computational modeling: contribution to risk assessment. Toxicol Sci 82:1–2. CrossRefGoogle Scholar
  21. Nabyvanetsʹ BY, Osadchyy VI, Osadcha NM, Nabyvanetsʹ YuB (2007) Analytical chemistry of surface waters. Naukova Dumka, Kiev, pp 338–340Google Scholar
  22. Nishikawa H, Sakai T (1995) Derivatization and chromatographic determination of aldehydes in gaseous and air samples. J Chromatogr A 710:159–165. CrossRefGoogle Scholar
  23. O’Brien PJ, Siraki AG, Shangari N (2005) Aldehyde sources, metabolism, molecular toxicity mechanisms, and possible effects on human health. Crit Rev Toxicol 35:609–662. CrossRefGoogle Scholar
  24. Pang X, Lewis AC, Shaw MD (2017) Analysis of biogenic carbonyl compounds in rainwater by stir bar sorptive extraction technique with chemical derivatization and gas chromatography-mass spectrometry. J Sep Sci 40:753–766. CrossRefGoogle Scholar
  25. Richardson SD, Plewa MJ, Wagner 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 636:178–242. CrossRefGoogle Scholar
  26. Salthammer T, Mentese S (2008) Comparison of analytical techniques for the determination of aldehydes in test chambers. Chemosphere 73:1351–1356. CrossRefGoogle Scholar
  27. Tessini C, Müller N, Mardones C, Meier D, Berg A, von Baer D (2012) Chromatographic approaches for determination of low-molecular mass aldehydes in bio-oil. J Chromatogr A 1219:154–160. CrossRefGoogle Scholar
  28. Uchiyama S, Hasegawa S (1999) A reactive and sensitive diffusion sampler for the determination of aldehydes and ketones in ambient air. Atmos Environ 33:1999–2005. CrossRefGoogle Scholar
  29. Vairavamurthy A, Roberts JM, Newman L (1992) Methods for determination of low molecular weight carbonyl compounds in the atmosphere. A review. Atmos Environ 26:1965–1993. CrossRefGoogle Scholar
  30. van Leeuwen SM, Hendriksen L, Karst U (2004) Determination of aldehydes and ketones using derivatization with 2,4-dinitrophenylhydrazine and liquid chromatography–atmospheric pressure photoionization-mass spectrometry. J Chromatogr A 1058:107–112. CrossRefGoogle Scholar
  31. Vogel M, Büldt A, Karst U (2000) Hydrazine reagents as derivatizing agents in environmental analysis—a critical review. Fresenius J Anal Chem 366:781–791. CrossRefGoogle Scholar
  32. Yukawa N, Takamura H, Matoba T (1993) Determination of total carbonyl compounds in aqueous media. JAOCS 70:881–884. CrossRefGoogle Scholar
  33. Zhan X-Q, Li D-H, Zhu Q-Z, Zheng H, Xu J-G (2000) Sensitive fluorimetric determination of formaldehyde by the co-quenching effect of formaldehyde and sulfite on the fluorescence of tetra-substituted amino aluminium phthalocyanine. Analyst 125:2330–2334. CrossRefGoogle Scholar
  34. Zhang H-J, Huang J-F, Wang H, Feng Y-Q (2006) Determination of low-aliphatic aldehyde derivatizatives in human saliva using polymer monolith microextraction coupled to high-performance liquid chromatography. Anal Chim Acta 565:129–135. CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Department of Ecology and Environment ProtectionUzhhorod National UniversityUzhhorodUkraine
  2. 2.Department of EcologyUniversity of Prešov in PrešovPrešovSlovak Republic
  3. 3.Department of Organic ChemistryUzhhorod National UniversityUzhhorodUkraine
  4. 4.Department of Analytical ChemistryUzhhorod National UniversityUzhhorodUkraine

Personalised recommendations