Direct
analysis of highly reactive volatile species such as the
aliphatic aldehydes as vital biomarkers remains a great challenge
due to difficulties in the sample pretreatment. To address such a
challenge, we herein report the development of a novel double-region
atmospheric pressure chemical ionization mass spectrometry (DRAPCI-MS)
method. The DRAPCI source implements a separated structural design
that uses a focus electrode to divide the discharge and ionization
region to reduce sample fragmentation in the ionization process. Counterflow
introduction (CFI) configuration was adopted in the DRAPCI source
to reduce background noise, while ion transmission efficiency was
optimized through simulating the voltage of the focus electrode and
the ion trajectory of the ion source. The limits of detection (LODs)
of four carbonyl compounds cyclohexanone, hexanal, heptanal, and octanal
by DRAPCI-MS were between 0.1 and 3 μg·m–3, approximately two to eight times lower than those by atmospheric
pressure chemical ionization mass spectrometry. Additionally, the
DRAPCI-MS method carried out effective in situ analyses of the volatile
components in expired milk and the exhaled breath of smokers, demonstrating
the DRAPCI-MS as a practical tool to analyze complex mixtures. The
DRAPCI-MS method provides a rapid, sensitive, and high-throughput
technique in the real-time analysis of gaseous small-molecule compounds.