Determination of volatile organic compounds in rainwater and dew water by head space solid-phase microextraction and gas chromatography/mass spectrometry

The optimization of the analysis of volatile organic compounds in atmospheric water samples, such as rainwater and dew water by head space solid-phase microextraction and gas chromatography/ mass spectrometry (HS SPME/GC/MS), was studied. The sensitivity of 23 VOCs, i.e. halogenated hydrocarbons and monocyclic aromatic hydrocarbons, was the highest after the extraction of VOCs in 16 mL of samples including 3.5 g of sodium chloride to SPME fiber (100μm PDMS) at 40°>C during 20 min of incubation. The repeatability of 1 ppb VOCs standard solution was below 10%, except for 1,2-dichloroethane (13%), and their detection limits ranged from 0.02 nM for dichloromethane to 0.30 nM for benzene. The recoveries of 22 VOCs, except for dichloromethane, ranged from 80 to 120% under the condition where 32 μL of 0.5 ppm VOC standard solution and 5 ppm fluorobenzene as an internal standard was added to 16 mL of atmospheric water samples. The application of the HS SPME/GC/MS method to the determination of VOCs in rainwater and dew water, which was collected in the western part of Tokyo, Hino, revealed that 6 chlorinated hydrocarbons (CHs) and five monocyclic hydrocarbons (MAHs) were detected, and the concentrations of MAHs were higher than those of CHs. Toluene was the dominant VOCs both in rainwater and dew water in Hino, and the volumeweighted concentrations of toluene in rainwater and dew water were 3.31 nM (n =39) and 5.21 nM (n =38), respectively. The results of this study made clear that the observed concentrations of VOCs in rainwater and dew water were considerably higher than the estimated concentrations, which were based on Henry's law equilibrium.