Vacuum-assisted headspace solid phase microextraction for monitoring ripening-induced changes in tomato volatile profile.

This work proposes, for the first time, the use of vacuum-assisted headspace solid phase microextraction (Vac-HS-SPME) for studying the free volatiles in tomato fruits. Initially, a comparative optimization between Vac-HS-SPME and regular HS-SPME was conducted, examining the effects of sampling time (15-60 min) and temperature (40 and 60°C) on the extraction of 29 target compounds from tomato puree samples. Compared to regular HS-SPME, sampling under vacuum resulted in the detection of nine additional analytes at 40°C, and an extra three at 60°C. The optimized methods (45 minutes sampling with Vac-HS-SPME at 40°C and regular HS-SPME at 60°C) were then successfully applied for the semi-quantitative comparison of free volatiles during on-plant ripening. These studies revealed an increase in volatiles across the six ripening stages considered (mature green, breaker, turning, pink, light red and red ripe) that was dominated by aldehydes. Compared to HS-SPME, the optimized Vac-HS-SPME showed substantial improvement in extraction efficiencies, and enabled the detection of key volatiles at earlier ripening stages, such as the breaker and turning stages. Overall, compared to the regular method, this study demonstrated that Vac-HS-SPME is a powerful approach that provides additional insights on free volatiles in fruits, even when sampling at lower temperatures.