Abstract Microbial volatile organic compounds (MVOCs) are important components of metabolites produced by microorganisms, and serve as chemical windows through which the fundamental information about the molecular basis of microbial activities is released. Understanding of the MVOCs, as well as the insights of the molecular basis associated with the MVOCs, provides a real-world capability to control and utilize microorganisms better than ever. MVOCs can be classified into species such as alcohol, aldehyde, organic acid, ester and ketone etc. Traditionally, successful detection of MVOCs requires sample pre-treatment such as separation and enrichment, because of the diversity of MVOCs in terms of physical/chemical property, concentration and matrices present in practical samples. In this review, the process and mechanism of formation of MVOCs are briefly summarized; recent progress made in applications of mass spectrometry for measurement of MVOCs are systematically reviewed, with emphases on the GC-MS and the comparison of different ionization techniques such as APCI, DESI, EESI, SDAPCI, SIFT and PTR. Clearly, novel ionization techniques such as EESI, SDAPCI and DESI requires no sample pretreatment, and provide rapid online analysis of MVOCs in real time. Prospectively, more advanced applications of these novel techniques based on mass spectrometry are anticipated.
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