Abstract
Stir bar sorptive extraction is a powerful technique for the extraction and analysis of organic compounds in aqueous matrices. Carbonyl compounds are ubiquitous components in rainwater, however, it is a major challenge to accurately identify and sensitively quantify carbonyls from rainwater due to the complex matrix. A stir bar sorptive extraction technique was developed to efficiently extract carbonyls from aqueous samples following chemical derivatization by O‐(2,3,4,5,6‐pentafluorobenzyl) hydroxylamine hydrochloride. Several commercial stir bars in two sizes were used to simultaneously measure 29 carbonyls in aqueous samples with detection by gas chromatography with mass spectrometry. A 100 mL aqueous sample was extracted by stir bars and the analytes on stir bars were desorbed into a 2 mL solvent solution in an ultrasonic bath. The preconcentration Coefficient for different carbonyls varied between 30 and 45 times. The limits of detection of stir bar sorptive extraction with gas chromatography mass spectrometry for carbonyls (10–30 ng/L) were improved by ten times compared with other methods such as gas chromatography with electron capture detection and stir bar sorptive extraction with high‐performance liquid chromatography and mass spectrometry. The technique was used to determine carbonyls in rainwater samples collected in York, UK, and 20 carbonyl species were quantified including glyoxal, methylglyoxal, isobutenal, 2‐hydroxy ethanal.
Highlights
Carbonyl compounds have been recognized to play a crucial role in atmospheric chemistry [1]
In cloud water some carbonyls such as formaldehyde, ethanal, acetone and propanal have been considered to be the precursors to secondary organic aerosol (SOA) formation through cloud processing, which may alter the ability of cloud-processed particles to act as cloud condensation nuclei (CCN) [1]
The higher volumes of PDMS coated on stir bar sorptive extraction (SBSE) compared to that of PDMS on SPME (0.5 μL) increase the amount of analyte extracted from the sample solution for the target analytes with low partition coefficients such as carbonyl PFBHA derivatives
Summary
Carbonyl compounds (carbonyls) have been recognized to play a crucial role in atmospheric chemistry [1]. Since GLY, MGLY, and some other carbonyls are common products from biogenic isoprene photooxidation and participate directly in the Abbreviations: CCN, cloud condensation nuclei; ECD, electron capture detection; GLY, glyoxal; MGLY, methylglyoxal; PDMS, polydimethylsiloxane; PFBHA, O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine; SBSE, stir bar sorptive extraction; SOA, secondary organic aerosol; VOC, volatile organic compound. Some sample treatment techniques have been employed to extract PFBHA-oxime derivatives from aqueous bulk including SPE [8], SPME [9,10], and stir bar sorptive extraction (SBSE) [11]. The higher volumes of PDMS coated on SBSE compared to that of PDMS on SPME (0.5 μL) increase the amount of analyte extracted from the sample solution for the target analytes with low partition coefficients such as carbonyl PFBHA derivatives. The environmental implications of biogenic carbonyls in rainwater are discussed in respect of CCN functions
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