Organic Tracers from Asphalt in Propolis Produced by Urban Honey Bees, Apis mellifera Linn.

Propolis is a gummy material produced by honey bees to protect their hives and currently has drawn the attention of researchers due to its broad clinical use. It has been reported, based only on observations, that honey bees also collect other non-vegetation substances such as paint or asphalt/tar to make propolis. Therefore, propolis samples were collected from bee hives in Riyadh and Al-Bahah, a natural area, Saudi Arabia to determine their compositional characteristics and possible sources of the neutral organic compounds. The samples were extracted with hexane and analyzed by gas chromatography-mass spectrometry. The results showed that the major compounds were (n) under bar -alkanes, (n) under bar -alkenes, methyl (n) under bar -alkanoates, long chain wax esters, triterpenoids and hopanes. The (n) under bar -alkanes (ranging from C-17 to C-40) were significant with relative concentrations varying from 23.8 to 56.8% (mean = 44.9 +/- 9.4%) of the total extracts. Their odd carbon preference index (CPI) ranged from 3.6 to 7.7, with a maximum concentration at heptacosane indicating inputs from higher plant vegetation wax. The relative concentrations of the (n) under bar -alkenes varied from 23.8 to 41.19% (mean = 35.6 +/- 5.1%), with CPI = 12.4-31.4, range from C-25 to C-35 and maximum at tritriacontane. Methyl (n) under bar -alkanoates, ranged from C-12 to C-26 as acids, with concentrations from 3.11 to 33.2%(mean = 9.6 +/- 9.5%). Long chain wax esters and triterpenoids were minor. The main triterpenoids were alpha- and beta-amyrins, amyrones and amyryl acetates. The presence of hopanes in some total extracts (up to 12.5%) indicated that the bees also collected petroleum derivatives from vicinal asphalt and used that as an additional ingredient to make propolis. Therefore, caution should be taken when considering the chemical compositions of propolis as potential sources of natural products for biological and pharmacological applications. Moreover, beekeepers should be aware of the proper source of propolis in the flight range of their bee colonies.