Changes of headspace volatiles in milk with riboflavin photosensitization

Effects of fluorescent light, riboflavin, ascorbic acid, sodium azide, and butylated hydroxyanisole (BHA) on the volatiles in milk at 4 °C were determined using a combination of headspace-solid phase microextraction (HS-SPME), gas chromatography (GC), and mass spectrometry (MS). Pentanal, hexanal, heptanal, and dimethyl disulfide were formed only in the milk stored under light and increased significantly as the duration of light exposure increased from 0 to 8 h and the concentration of added riboflavin increased from 5 to 50 ppm (P < 0.05). As fat content in milk increased, peak areas of pentanal, hexanal, and heptanal increased significantly (P < 0.05) while those of dimethyl disulfide did not change significantly (P > 0.05). Sodium azide prevented the formation of dimethyl disulfide in milk, implying that dimethyl disulfide can be formed through singlet oxygen oxidation (type II pathway). Addition of ascorbic acid and BHA reduced the formation of hexanal, heptanal, and dimethyl disulfide significantly (P < 0.05). Generation mechanisms of pentanal seem to be different from those of hexanal and heptanal in milk. Both singlet oxygen oxidation (type II pathway) and free radicals (type I pathway) play important roles in the formation of light-induced volatiles in milk.