Methanethiol, an Off-Flavor Produced from the Thermal Treatment of Mandarin Juices: A Study of Citrus Sulfur Volatiles

The off-flavor produced after thermal stabilization of mandarin (Citrus reticulata, Blanco) juices has limited the production of commercial juices. Methanethiol, a putrid-smelling sulfur volatile, has been identified for the first time in heated mandarin juices. Identification was achieved using a combination of capillary gas chromatography with two dissimilar columns and a dual sulfur-specific pulsed flame photometric detector and selected ion mass spectrometry detection. Static headspace solid-phase microextraction quantitation found that average odor activity values (OAVs) in heated juices were 25.5 for methanethiol compared to 10.8 for dimethyl sulfide. OAVs for methanethiol and dimethyl sulfide in fresh juices were ND (not detected) and 5.5, respectively. Hydrogen sulfide, carbonyl sulfide, carbon disulfide, and dimethyl disulfide were also identified and quantitated. Thermal decomposition studies of nonvolatile sulfur-containing potential precursors indicated that methionine was the major source of methanethiol. Additional heating studies with model juices demonstrated that ascorbic acid greatly accelerated the formation of methanethiol and methional, as well as dimethyl di and tri sulfides.