HPLC-DAD-MSn characterisation of carotenoids from apricots and pumpkins for the evaluation of fruit product authenticity

Carotenoids including carotenoid esters from six apricot (Prunus armeniaca L.) cultivars and from eight cultivars from three pumpkin species (Cucurbita maxima Duch., Cucurbita pepo L., and Cucurbita moschata Duch.) were extracted without saponification, separated on a C-30 reversed-phase column and characterised by high-performance liquid chromatography/atmospheric pressure chemical ionisation–mass spectrometry (LC–MS). The predominant free carotenoids were quantified by HPLC with diode array detection. In contrast to previously published data, α-carotene could not be detected in apricots. Although the pumpkins showed significant differences in their free carotenoid profiles, major unesterified compounds different from those found in apricots could be determined. However, due to the natural heterogeneity, authentication of the apricot products cannot be accomplished exclusively using the profile of free carotenoids. Therefore, the investigations were extended to carotenoid esters. The xanthophyll ester profiles in pumpkins significantly differed from those in apricots in that the latter also contained both saturated and unsaturated fatty acids, whereas in pumpkins exclusively saturated fatty acids were detected. Admixtures of lower cost pumpkins could be detected in quantities of ⩾5% by increased contents of lutein and zeaxanthin, and by the appearance of antheraxanthin and α-carotene, respectively, depending on the added pumpkin cultivar, as well as the presence of characteristic lutein and antheraxanthin esters. However, pronounced differences in the carotenoid profiles of the investigated pumpkins and the partly minor amount of characteristic compounds lead to limitations of the detection of 5% level of admixture of pumpkin to apricot and of the method in general.