Analysis of 31 Hydrazones of Carbonyl Compounds by RRLC-UV and RRLC-MS(/MS): A Comparison of Methods

Aldehydes and ketones are volatile organic compounds (VOC) emitted into the atmosphere by a large number of natural and anthropogenic sources. Carbonyl compounds (CC) are atmospheric pollutants with known damaging effects for the human’s health. In this work, the separation of 31 carbonyl compounds (CC) in their 2,4-dinitrophenylhydrazones form was optimized by rapid resolution liquid chromatography in 9 minutes and simultaneously detected by ultraviolet and mass spectrometry with an APCI(−) as ionization source. The mass spectra of hydrazones presented the [M-H]− ions as base peak, but the MS/MS spectra showed fragments related to different structural classes of aldehydes and ketones, representing an important tool to assist structure elucidation of unknown CC in real samples. Multiple reactions monitoring (MRM) improved the sensitivity and selectivity for the quantitation method. Analytical parameters using both UV and MS (linearity, determination coefficients, detection limits, and sensitivity) were compared. The detection methods are complementary and a powerful analytical tool for the detection and quantitation of CC in complex environmental samples.

[1]  M. R. Rodrigues,et al.  Occupational exposure to formaldehyde in an institute of morphology in Brazil: a comparison of area and personal sampling , 2012, Environmental Science and Pollution Research.

[2]  L. Guarieiro,et al.  Acetaldehyde and formaldehyde concentrations from sites impacted by heavy-duty diesel vehicles and their correlation with the fuel composition: Diesel and diesel/biodiesel blends , 2012 .

[3]  A. Lewis,et al.  Carbonyl compounds in gas and particle phases of mainstream cigarette smoke. , 2011, The Science of the total environment.

[4]  F. Gosetti,et al.  Simultaneous determination of thirteen polycyclic aromatic hydrocarbons and twelve aldehydes in cooked food by an automated on-line solid phase extraction ultra high performance liquid chromatography tandem mass spectrometry. , 2011, Journal of chromatography. A.

[5]  A. D. Pereira Netto,et al.  Evaluation of C1–C13 carbonyl compounds by RRLC-UV in the atmosphere of Niterói City, Brazil , 2011 .

[6]  X. Lee,et al.  Temporal variations of atmospheric carbonyls in urban ambient air and street canyons of a Mountainous city in Southwest China , 2010 .

[7]  Jiamo Fu,et al.  A method of detecting carbonyl compounds in tree leaves in China , 2010, Environmental science and pollution research international.

[8]  A. D. Pereira Netto,et al.  Optimization and comparison of HPLC and RRLC conditions for the analysis of carbonyl-DNPH derivatives. , 2010, Talanta.

[9]  Manuel Silva,et al.  Liquid chromatography-tandem mass spectrometry for the determination of low-molecular mass aldehydes in human urine. , 2010, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[10]  J. D. de Andrade,et al.  Determination of carbonyl compounds in the atmosphere of charcoal plants by HPLC and UV detection. , 2008, Journal of separation science.

[11]  Jiamo Fu,et al.  Determination of carbonyl compounds in the atmosphere by DNPH derivatization and LC-ESI-MS/MS detection. , 2007, Talanta.

[12]  H. Sakugawa,et al.  Rapid and Highly Sensitive Determination of Low-Molecular-Weight Carbonyl Compounds in Drinking Water and Natural Water by Preconcentration HPLC with 2,4-Dinitrophenylhydrazine , 2006, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[13]  T. Shibamoto,et al.  Determination of toxic carbonyl compounds in cigarette smoke , 2006, Environmental toxicology.

[14]  J. Kohoutek,et al.  Determination of volatile organic compounds in the atmosphereand their influence on ozone formation. , 2006 .

[15]  J. Mazzeo,et al.  Advancing LC Performance with Smaller Particles and Higher Pressure , 2005 .

[16]  U. Karst,et al.  Determination of aldehydes and ketones using derivatization with 2,4-dinitrophenylhydrazine and liquid chromatography-atmospheric pressure photoionization-mass spectrometry. , 2004, Journal of chromatography. A.

[17]  K. Imamura,et al.  Analysis of Aliphatic and Aromatic Carbonyl Compounds in Ambient Air by LC/MS/MS , 2004, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[18]  Massimo Corradi,et al.  Determination of patterns of biologically relevant aldehydes in exhaled breath condensate of healthy subjects by liquid chromatography/atmospheric chemical ionization tandem mass spectrometry. , 2003, Rapid communications in mass spectrometry : RCM.

[19]  J. B. D. Andrade,et al.  Compostos carbonílicos atmosféricos: fontes, reatividade, níveis de concentração e efeitos toxicológicos , 2002 .

[20]  C. Vinckier,et al.  HPLC–MS determination of the oxidation products of the reaction between α- and β-pinene and OH radicals , 2002 .

[21]  F. Frimmel,et al.  Method optimization for the determination of carbonyl compounds in disinfected water by DNPH derivatization and LC–ESI–MS–MS , 2002, Analytical and bioanalytical chemistry.

[22]  M. Oehme,et al.  Unusual MSn fragmentation patterns of 2,4‐dinitrophenylhydrazine and its propanone derivative , 2001 .

[23]  J. A. Beukes,et al.  HPLC combined with multiple mass spectrometry (MSn): an alternative for the structure elucidation of compounds and artefacts found in smog chamber samples. , 2001, Journal of environmental monitoring : JEM.

[24]  S. Richardson,et al.  Application of DNPH Derivatization with LC/MS to the Identification of Polar Carbonyl Disinfection Byproducts in Drinking Water , 2000 .

[25]  C. Vinckier,et al.  Identification of the oxidation products of the reaction between alpha-pinene and hydroxyl radicals by gas and high-performance liquid chromatography with mass spectrometric detection. , 2000, Journal of chromatography. A.

[26]  A. Bruins,et al.  Atmospheric pressure photoionization: an ionization method for liquid chromatography-mass spectrometry , 2000, Analytical chemistry.

[27]  T. Yoneno,et al.  Trace analysis of carbonyl compounds by liquid chromatography-mass spectrometry after collection as 2,4-dinitrophenylhydrazine derivatives. , 1999, Journal of chromatography. A.

[28]  E. Grosjean,et al.  Liquid Chromatography Analysis of Carbonyl (2,4-Dinitrophenyl)hydrazones with Detection by Diode Array Ultraviolet Spectroscopy and by Atmospheric Pressure Negative Chemical Ionization Mass Spectrometry. , 1999, Analytical chemistry.

[29]  U. Karst,et al.  HPLC-APCI-MS with calibration based on stable isotope-labelled internal standards for the quantification of carbonyls in air samples , 1999 .

[30]  M. Oehme,et al.  Structure Elucidation of 2,4-Dinitrophenylhydrazone Derivatives of Carbonyl Compounds in Ambient Air by HPLC/MS and Multiple MS/MS Using Atmospheric Chemical Ionization in the Negative Ion Mode. , 1998, Analytical chemistry.

[31]  E. Grosjean,et al.  Carbonyl Collection Efficiency of the DNPH-Coated C18 Cartridge in Dry Air and in Humid Air , 1996 .