Characterisation and optimisation of a method for the detection and quantification of atmospherically relevant carbonyl compounds in aqueous medium

Abstract

Abstract. Carbonyl compounds are ubiquitous in the atmosphere and either emitted primarily from anthropogenic and biogenic sources or they are produced secondarily from the oxidation of volatile organic compounds (VOC). Despite a number of studies about the quantification of carbonyl compounds a comprehensive description of optimised methods is scarce for the quantification of atmospherically relevant carbonyl compounds. Thus a method was systematically characterised and improved to quantify carbonyl compounds. Quantification with the present method can be carried out for each carbonyl compound sampled in the aqueous phase regardless of their source. The method optimisation was conducted for seven atmospherically relevant carbonyl compounds including acrolein, benzaldehyde, glyoxal, methyl glyoxal, methacrolein, methyl vinyl ketone and 2,3-butanedione. O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was used as derivatisation reagent and the formed oximes were detected by gas chromatography/mass spectrometry (GC/MS). The main advantage of the improved method presented in this study is the low detection limit in the range of 0.01 and 0.17 μmol L−1 depending on carbonyl compounds. Furthermore best results were found for extraction with dichloromethane for 30 min followed by derivatisation with PFBHA for 24 h with 0.43 mg mL−1 PFBHA at a pH value of 3. The optimised method was evaluated in the present study by the OH radical initiated oxidation of 3-methylbutanone in the aqueous phase. Methyl glyoxal and 2,3-butanedione were found to be oxidation products in the samples with a yield of 2% for methyl glyoxal and 14% for 2,3-butanedione.

Analytical methodologies for oxidized organic compounds in the atmosphere

“…Possible reagents are O-methylhydroxylamine (MHA), 34,87,89,95,101 O-benzylhydroxylamine (BHA), 66,68,90 O-tert-butylhydroxylamine, 104,105 and O-(2,3,4,5,6-pen-tauorobenzyl)hydroxylamine (PFBHA). 82,106 Oxime derivatives have been mainly applied for GC analyses, but they can also be employed in LC. 68 Oxime derivatization can be performed in an organic solvent (MeOH, ACN, DCM, and their mixtures) or in an aqueous matrix.…”