African shea butter, a vegetable fat produced from the seeds of Vitellaria paradoxa C.F. Gaertn. (syn. Butyrospermum parkii L.), Sapotaceae, is a unique natural product of African countries and is of great nutritional and commercial significance. The volatile compounds of various shea butter samples were analysed to investigate the influence of differences in manufacturing (boiling/roasting or combined procedures) on the headspace composition and with regard to the different origin of the samples. Volatile compounds were analysed by using gas chromatography–mass spectrometry after headspace solid phase microextraction (HS-SPME). Qualitative and semi-quantitative patterns of volatile compounds investigated in this study were composed of fatty acids degradation products, e.g. acetic and hexanoic acid, carbonyl compounds (hexanal, heptanal, trans-2-heptenal, 2,4-heptadienal), 2-pentylfurane, processing compounds like furfural as well as glycerol and residue compounds from technical processing steps including milling. Comparison of the volatile profile of 16 different shea butters from four African countries showed that processing steps including drying of kernels before producing the fat and additional roasting procedures influence shea butter headspace composition significantly.
Several nut oil varieties mainly used as culinary and overall healthy food ingredients were subject of the present study. Headspace solid-phase microextraction combined with gas chromatography-mass spectrometry was employed in order to determine the qualitative composition of volatile compounds. Furthermore, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry was used in order to assess the profiles and relative composition of the prevalent triacylglycerols (TAG) within the oils. The headspace of the majority of oil samples was dominated by high contents of acetic acid (up to 42%) and hexanal (up to 32%). As nut oils are typically gained by cold-pressing from previously roasted nuts, characteristic pyrazine derivatives as well as degradation products of long-chain fatty acids were detected. TAG analysis of these oils revealed a quite homogeneous composition dominated by components of the C-52 and C-54 group composed mainly of oleic (18: 1), linoleic (18:2), stearic (18:0) and palmitic (16:0) acid residues representing together between 65 and 95% of the investigated nut oils. The TAG profiles showed characteristic patterns which can be used as 'fingerprints' of the genuine oils. Nut oils exhibiting quite similar fatty acid composition (e.g. hazelnut, pistachio and beech oil) could be clearly discriminated based on TAG showing significant differences between the oils.
Some typical original Indian edible and non-edible fatty plant oils were subject of our investigations. Fundamental research was done on analyzing volatile compounds using HS-SPME-GC-MS. In addition, a sensorial evaluation was applied to receive data on the smell of the samples. Furthermore, the typical and prevailing triacylglycerols (TAG) were investigated by MALDI-TOF-MS. Mass spectra reflect the TAG profiles of the whole oil samples based on the detection of [M+Na](+) ions. Oil samples exhibit quite unique TAG profiles, which are suitable for rapid characterization of the original plant oils. The fatty acid composition of the corresponding TAG structures was calculated using lipid analysis software based on the known fatty acid composition. Relative quantification of TAG components was in good agreement with the literature, in case appropriate data are available so far.
Grape seed oil (Oleum vitis viniferae) representing a promising plant fat, mainly used for culinary and pharmaceutical purposes as well as for various technical applications, was subject of the present investigation. HS-SPME-GC-MS was applied to study volatile compounds in several seed oil samples from different grape oils. The triacylglycerol (TAG) composition of these oils was analyzed by MALDI-TOF-MS/MS. In addition the total phenol content and the antioxidant capacity (using TEAC) of these oils were determined. The headspace of virgin grape oils from white and red grapes was dominated by ethyl octanoate (up to 27.5% related to the total level of volatiles), ethylacetate (up to 25.0%), ethanol (up to 22.7%), acetic acid (up to 17.2%), ethyl hexanoate (up to 17.4%) and 3-methylbutanol (up to 11.0%). Triacylglycerol composition was found to be dominated by LLL (up to 41.8%), LLP (up to 24.3%), LLO (up to 16.3%) and LOO (up to 11.7%), followed by LOP (up to 9.3%) and LOS/OOO (up to 4.3%). Total phenol content ranged between 59μg/g and 115.5μg/g GAE. Antioxidant capacity (TEAC) was analyzed to range between 0.09μg/g and 1.16μg/g.
Although poppy seed oil is an expensive article of trade, no literature about identification methods for adulteration with cheaper vegetable oils, like sunflower oil, has been published. This kind of adulteration is a challenge for routine analytical methods, such as the determination of fatty acid composition, because of almost similar fatty acid ratios. The detection of adulteration of poppy seed oils with sunflower oils at different levels (5-40%, w/w) by using SPME-GC-MS and MALDI-ToF-MS is the subject of our investigation. With the mentioned SPME-GC-MS method, it was possible to detect an admixture of sunflower oils in all relevant (5-40%) amounts by using alpha-pinene as a marker compound. Admixture of sunflower oil with high levels of triolein (high-oleic acid type) could be undoubtedly detected by MALDI-MS down to the 5-10% level. In contrast, adulteration of pure poppy seed oil by "standard" sunflower oils remained indistinguishable using this MALDI-MS.
Shea butter is used as an edible vegetable fat in many African countries. It can be utilized as a substitute or complete replacement for cocoa butter in various applications and plays an important role in traditional African medicinal practice. Although detection of volatile compounds by solid-phase micro-extraction gas-chromatography mass-spectroscopy (SPME-GC-MS) is a very reliable and reproducible technique, which can be used as an important part of authenticity checking, production monitoring and contamination detection, no published data about volatile compounds of shea butter are available so far. In this investigation, the characteristic volatiles in the headspace of original African shea butter samples were identified by using SPME-capillary-GC coupled to a mass selective detector. Almost 100 different volatile components were identified, e.g. fatty acids, saturated and unsaturated aldehydes and ketones, terpenes, and typical Maillard reaction products such as methylfuranes and pyrazines. Furthermore, the samples have been olfactorily evaluated by a panel of professional flavorists and trained analytical chemists. It can be stated that variations in processing conditions of shea butter result in considerable differences in the composition of headspace volatiles, detected by SPME-GC-MS and human olfaction.
Linseed (Linum usitatissimum, L.) and camelina (Camelina sativa, L.) are ancient crops containing seed oils with a high potential for nutritional, medicinal, pharmaceutical and technical applications. In the present study, linseed and camelina oils of plant varieties grown under Central European climate conditions were examined with respect to their volatile and triacylglycerol (TAG) components. Solid-phase microextraction was applied to the study of volatile compounds of several linseed and camelina oils, which have not been described prior to this publication. Hexanol (6.5-20.3% related to the total level of volatiles), trans-2-butenal (1.3-5.0%) and acetic acid (3.6-3.8%) could be identified as the main volatile compounds in the linseed oil samples. Trans-2-butenal (9.8%) and acetic acid (9.3%), accompanied by trans,trans-3,5-octadiene-2-one (3.8%) and trans, trans-2,4-heptadienal (3.6%), dominated the headspace of the examined camelina oil samples. TAG were analysed by MALDI-RTOF-MS and ESI-IT-MIS, providing information about the total TAG composition of the oils as well as the fatty acid composition of the individual components. More than 20 TAG could be identified directly from whole linseed oil samples, mainly composed of linolenic (18:3), linoleic (18:2) and oleic (18:1) acid, and to a lesser degree of stearic (18:0) and palmitic (16:0) acid. While in linseed these TAG comprise more than 60% of the oils, Camelina sativa exhibited a wider range of more than 50 constituents, with a considerable amount (> 35%) of TAG containing gadoleic (20:1) and eicosadienoic (20:2) acid.
Poppy seed oil (Oleum Papaveris Seminis) is used for culinary and pharmaceutical purposes, as well as for making soaps, paints, and varnishes. Astonishingly, hardly anything was yet known about the volatile compounds of this promising comestible. Likewise, there are no current published data about the triglyceride (TAG) composition of poppy seed oils available. In this investigation solid-phase microextraction (SPME) with DVB/Carboxen/PDMS Stable-Flex fiber was applied to the study of volatile compounds of several seed oil samples from Papaver somniferum L. (Papaveraceae). 1-Pentanol (3.3-4.9%), 1-hexanal (10.9-30.9%), 1-hexanol (5.3-33.7%), 2-pentylfuran (7.2-10.0%), and caproic acid (2.9-11.5%) could be identified as the main volatile compounds in all examined poppy seed oil samples. Furthermore, the TAG composition of these oils was analyzed by MALDI-ReTOF- and ESI-IT-MS/MS. The predominant TAG components were found to be composed of linoleic, oleic, and palmitic acid, comprising approximately 70% of the oils. TAG patterns of the different poppy varieties were found to be very homogeneous, showing also no significant differences in terms of the applied pressing method of the plant seeds.
The volatile flavor compounds of roasted Italian chestnuts, which have not been studied prior to this report, were determined by capillary gas-chromatography with a mass selective detector. Samples were obtained by SPME directly from the headspace of freshly roasted and ground chestnuts as well as by previous extraction with dichloromethane. Monoterpenes and derivatives of butane, pentane, hexane, and heptane were identified as important aroma impact compounds. γ-Butyrolactone (12.8%), γ-terpinene (9.2%), furfural (6.3%), benzaldehyde (7.2%) and 4-methyl-2-pentanone (5.3%) were found in concentrations higher than 5.0% (calculated as % peak area of GC-MS analysis using a nonpolar column).
Varroa destructor, an ectoparasitic mite, is one of the major pests of honeybees in many parts of the world. In order to keep bee colonies alive and productive, effective biological, biotechnical, or acaricidal control measures are necessary. Oxalic acid is one substance under discussion to replace synthetic acaricides (e.g. pyrethroids, organophosphates) to minimize the risk of residues in bee products. The application of oxalic acid based solutions (Bienenwohl or a self-prepared oxalic acid solution with sugar) to control Varroa destructor resulted in no relevant changes in the oxalic acid content of honey produced the following year, compared with honey samples from untreated colonies from the same location. The range of oxalic acid content in honey was 5–68 mg/kg in oxalic acid treated and 5–65 mg/kg in untreated colonies. The oxalic acid content of the honey was positively correlated with its electrical conductivity and thus with its original nectar or honeydew source.