Generation of sub-ppb level vapor phase mixtures of biogenic volatile organic compounds from liquid phase standards and stepwise characterization of their volatilization properties by thermal desorption–gas chromatography–mass spectrometry

• The quantitation of biogenic volatile organic compounds (BVOCs) is prone to diverse sources of biases.
• A method was developed to generate ambient level concentration of vapor-phase BVOC standards.
• The reliability of the method was also investigated to explain liquid-gas partitioning behavior of BVOCs.
• These data were also used to compare vaporization characteristics between all selected BVOCs and AVOCs.

In the analysis of biogenic volatile organic compounds (BVOCs) in ambient air, preparation of a sub-ppb level standard is an important factor. This task is very challenging as most BVOCs (e.g., monoterpenes) are highly volatile and reactive in nature. As a means to produce sub-ppb gaseous standards for BVOCs, we investigated the dynamic headspace (HS) extraction technique through which their vapors are generated from a liquid standard (mixture of 10 BVOCs: (1) α-pinene, (2) β-pinene, (3) 3-carene, (4) myrcene, (5) α-phellandrene, (6) α-terpinene, (7) R-limonene, (8) γ-terpinene, (9) p-cymene, and (10) Camphene) spiked into a chamber-style impinger. The quantification of BVOCs was made by collection on multiple-bed sorbent tubes (STs) and subsequent analysis by thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS). Using this approach, sub-ppb level mixtures of gaseous BVOCs were generated at different sweep cycles. The mean concentrations of 10 BVOCs generated from the most stable conditions (i.e., in the third sweep cycle) varied in the range of 0.37 ± 0.05 to 7.27 ± 0.86 ppb depending on the initial concentration of liquid standard spiked into the system. The reproducibility of the gaseous BVOCs generated as mixture standards, if expressed in terms of relative standard error using the concentration datasets acquired under stable conditions, ranged from 1.64 (α-phellandrene) to 9.67% (R-limonene).