Genetic characterization of an almond germplasm collection and volatilome profiling of raw and roasted kernels.

Almond is appreciated for its nutraceutical value and for the aromatic profile of the kernels. In this work, an almond collection composed of 96 Sicilian accessions complemented with 10 widely cultivated cultivars was phenotyped for the production of volatile organic compounds using a proton-transfer time-of-flight mass spectrometer and genotyped using the Illumina Infinium®18 K Peach SNP array. The profiling of the aroma was carried out on fresh and roasted kernels enabling the detection of 150 mass peaks. Sixty eight, for the most related with sulfur compounds, furan containing compounds, and aldehydes formed by Strecker degradation, significantly increased during roasting, while the concentration of fifty-four mass peaks, for the most belonging to alcohols and terpenes, significantly decreased. Four hundred and seventy-one robust SNPs were selected and employed for population genetic studies. Structure analysis detected three subpopulations with the Sicilian accessions characterized by a different genetic stratification compared to those collected in Apulia (South Italy) and the International cultivars. The linkage-disequilibrium (LD) decay across the genome was equal to r2 = 0.083. Furthermore, a high level of collinearity (r2 = 0.96) between almond and peach was registered confirming the high synteny between the two genomes. A preliminary application of a genome-wide association analysis allowed the detection of significant marker-trait associations for 31 fresh and 33 roasted almond mass peaks respectively. An accurate genetic and phenotypic characterization of novel germplasm can represent a valuable tool for the set-up of marker-assisted selection of novel cultivars with an enhanced aromatic profile.

Ethnicity, gender and physiological parameters: Their effect on in vivo flavour release and perception during chewing gum consumption.

In this study, the impact of physiological parameters, ethnicity and gender on flavour perception and flavour release of chewing gum was investigated. Proton Transfer Reaction Mass Spectrometry in-nose monitoring of volatile organic compounds was coupled to discontinuous time intensity sensory evaluation for mint flavour and sweetness perception. Each of the 29 subjects, 14 European and 15 Chinese panelists (13 male and 16 females, age 24 ±â€¯1.4 years old) consumed the samples in triplicates. Physiological parameters (oral cavity volume, salivary flow, acetone and isoprene concentration and fungiform papillae density) were measured. Significant differences for in vivo flavour release between Chinese and European panelists after 90 s of consumption and after the gum was removed from the mouth were found. Significant differences were observed also in flavour and sweetness perception while no gender effect was detected. In this work, for the first time an effect of ethnicity on in-nose flavour release monitored through PTR-MS was noticed during chewing gum consumption, in agreement with the findings from sensory evaluation. Single physiological parameters do not explain the relation between flavour in nose release and perception during consumption.

Evaluation of PTR-ToF-MS as a tool to track the behavior of hop-derived compounds during the fermentation of beer.

Hop-derived volatile organic compounds (VOCs) play an important role in the flavor and aroma of beer, despite making up a small percentage of the overall profile. To understand the changes happening during fermentation, proton transfer reaction-time of flight-mass spectrometry (PTR-ToF-MS) was applied for the first time in brewing science to directly measure the changes in hop-derived VOCs during the fermentation of four different worts containing one of two aroma hops in combination with one of two yeast biotypes. PTR-ToF-MS successfully detected and tracked mass-to-charge ratios (m/z) arising from interactions between the different yeast strains and the hop cultivars. Differences were observed in the dynamic VOC profiles between different beer treatments for m/z such as m/z 145.121 (ethyl hexanoate) and m/z 173.153 (isoamyl isovalerate or ethyl octanoate). The ability to monitor changes in VOCs during fermentation provides valuable information on the priority of production and transformation reactions by yeast.

Rapid and noninvasive quality control of anhydrous milk fat by PTR-MS: The effect of storage time and packaging.

In this study, proton transfer reaction-mass spectrometry (PTR-MS), coupled with a time-of-flight mass analyzer and a multipurpose automatic sampler, was evaluated as a rapid and nondestructive tool for the quality control of anhydrous milk fat. Anhydrous milk fats packed in cardboard and bag-in-box were compared during refrigerated shelf life at 4°C for 9 months. Anhydrous milk fat samples were taken at 120, 180, and 240 days and measured by PTR-MS during storage at 50°C for 11 days. Univariate and multivariate data analysis were performed in order to classify samples according to the packaging type and compare aromatic profiles. Markers related to both packaging and storage duration were identified, and all stored samples were clearly distinguishable from reference fresh samples. Significant differences in some key butter aroma compounds such as 2-pentanone, 2-heptanone, 2/3-methylbutanal, acetoin, and butanoic acid were observed between different types of packaging. During the refrigerated storage, differences related to packaging are more evident, while during the storage at 50°C, the fat oxidation induced by the high temperature becomes the most relevant phenomenon independently of the packaging type. These results indicate the importance of avoiding anhydrous milk fat storage at 50°C for long times during industrial production processes. All together data demonstrated the viability of PTR-MS as a rapid and high-sensitivity tool in agroindustry quality control program.

Proton transfer reaction time-of-flight mass spectrometry: A high-throughput and innovative method to study the influence of dairy system and cow characteristics on the volatile compound fingerprint of cheeses.

The aim of this work was to study the effect of dairy system and individual cow-related factors on the volatile fingerprint of a large number of individual model cheeses analyzed by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS). A total of 1,075 model cheeses were produced using milk samples collected from individual Brown Swiss cows reared in 72 herds located in mountainous areas of Trento province (Italy). The herds belonged to 5 main dairy systems ranging from traditional to modern and the cows presented different daily milk yields (24.6±7.9kg × d(-1)), stages of lactation (199±138 d in milk), and parities (2.7±1.8). The PTR-ToF-MS revealed 619 peaks, of which the 240 most intense were analyzed, and 61 of these were tentatively attributed to relevant volatile organic compounds on the basis of their fragmentation patterns and data from the literature. Principal component analysis was used to convert the multiple responses characterizing the PTR-ToF-MS spectra into 5 synthetic variables representing 62% of the total information. These principal components were related to groups of volatile compounds tentatively attributed to different peaks and used to investigate the relationship of the volatile compound profile obtained by PTR-ToF-MS to animal and farm characteristics. Lactation stage is related to 4 principal components which brought together 52.9% of the total variance and 57.9% of the area of analyzed peaks. In particular, 2 principal components were positively related to peaks tentatively attributed to aldehydes and ketones and negatively related to alcohols, esters, and acids, which displayed a linear increase during lactation. The second principal component was affected by dairy system; it was higher in the modern system in which cows received total mixed rations. The third principal component was positively related to daily milk production. In summary, we report the first application of this innovative, high-throughput technique to study the effects of dairy system and individual animal factors on volatile organic compounds of model cheeses. Individual cheesemaking procedures together with this spectrometric technique open new avenues for genetic selection of dairy species with respect to both milk and cheese quality.

Effects of dairy system, herd within dairy system, and individual cow characteristics on the volatile organic compound profile of ripened model cheeses.

The objective of this work was to study the effect of dairy system, herd within dairy system, and characteristics of individual cows (parity, days in milk, and daily milk yield) on the volatile organic compound profile of model cheeses produced under controlled conditions from the milk of individual cows of the Brown Swiss breed. One hundred fifty model cheeses were selected from 1,272 produced for a wider study of the phenotypic and genetic variability of Brown Swiss cows. In our study, we selected 30 herds representing 5 different dairy systems. The cows sampled presented different milk yields (12.3-43.2kg/d), stages of lactation (10-412 d in milk), and parity (1-7). In total, 55 volatile compounds were detected by solid-phase microextraction and gas chromatography-mass spectrometry, including 14 alcohols, 13 esters, 11 free fatty acids, 8 ketones, 4 aldehydes, 3 lactones, 1 terpene, and 1 pyrazine. The most important sources of variation in the volatile organic profiles of model cheeses were dairy system (18 compounds) and days in milk (10 compounds), followed by parity (3 compounds) and milk yield (5 compounds). The model cheeses produced from the milk of tied cows reared on traditional farms had lower quantities of 3-methyl-butan-1-ol, 6-pentyloxan-2-one, 2-phenylethanol, and dihydrofuran-2(3H)-one compared with those reared in freestalls on modern farms. Of these, milk from farms using total mixed rations had higher contents of alcohols (hexan-1-ol, octan-1-ol) and esters (ethyl butanoate, ethyl pentanoate, ethyl hexanoate, and ethyl octanoate) and lower contents of acetic acid compared with those using separate feeds. Moreover, dairy systems that added silage to the total mixed ration produced cheeses with lower levels of volatile organic compounds, in particular alcohols (butan-1-ol, pentan-1-ol, heptan-1-ol), compared with those that did not. The amounts of butan-2-ol, butanoic acid, ethyl-2-methylpropanoate, ethyl-3-methylbutanoate, and 6-propyloxan-2-one increased linearly during lactation, whereas octan-1-ol, 3-methyl-3-buten-1-ol, 2-butoxyethanol, 6-pentyloxan-2-one, and 2,6-dimethylpyrazine showed a more complex pattern during lactation. The effect of the number of lactations (parity) was significant for octan-1-ol, butanoic acid, and heptanoic acid. Finally, concentrations of octan-1-ol, 2-phenylethanol, pentanoic acid, and heptanoic acid increased with increasing daily milk yield, whereas dihydrofuran-2(3H)-one decreased. In conclusion, the volatile organic compound profile of model cheeses from the milk of individual cows was affected by dairy farming system and stage of lactation and, to lesser extent, by parity and daily milk yield.

Effect of IGF-II genotype and pig rearing system on the final characteristics of dry-cured Iberian hams.

The effect of the IGF-II genotype (AG vs. GG) on the morphological and compositional parameters, the fatty acid composition of intramuscular fat, the odour concentration (analysed by dynamic olfactometry) and the volatile compound profile (analysed by proton transfer reaction time-of-flight mass spectrometry) of dry-cured Iberian ham was studied for the first time, and compared to the effect of pig rearing system (high-oleic concentrated feed vs. acorn and grass). The IGF-II genotype had no effect on most variables. However, it influenced the concentration of some odorants (methanethiol and octanal), although it did not affect odour concentration. Conversely, the rearing system had a significant effect on a large number of ham variables. Results indicate a negligible effect of the IGF-II genotype on the final ham quality and confirm that the rearing system has a marked effect.

Effect of the pig rearing system on the final volatile profile of Iberian dry-cured ham as detected by PTR-ToF-MS.

The volatile compound profile of dry-cured Iberian ham lean and subcutaneous fat from pigs fattened outdoors on acorn and pasture (Montanera) or on high-oleic concentrated feed (Campo) was investigated by proton transfer reaction time-of-flight mass spectrometry. In addition to the usual proton transfer ionization the novel switchable reagent ions system was implemented which allows the use of different precursor ions (H(3)O(+), NO(+) and O(2)(+)). The analysis of the lean and subcutaneous fat volatile compounds allowed a good sample discrimination according to the diet. Differences were evident for several classes of compounds: in particular, Montanera hams showed higher concentrations of aldehydes and ketones and lower concentrations of sulfur-containing compounds compared to Campo hams. The use of NO(+) as precursor ion confirmed the results obtained with H(3)O(+) in terms of classification capability and provides additional analytical insights.

Measuring odour emission and biofilter efficiency in composting plants by proton transfer reaction-mass spectrometry.

PTR-MS (Proton Transfer Reaction-Mass Spectrometry) is an innovative technique that allows the rapid detection of most volatile organic compounds (VOCs) with high sensitivity (sub-ppb) and by direct injection. We describe here the possible use of PTR-MS in waste managements and composting plants both for the real time monitoring of volatile emissions and, after calibration with olfactometric assessments, for the instrumental determination of odour concentration. Beside a short description of the technique, we will report on the calibration of PTR-MS data with olfactometric assessment of odour concentration showing the possibility of a relatively good estimation of odour concentration by instrumental data. We will also show how the rapid PTR-MS fingerprint can be used to visualise the overall effect of a biofilter on the VOCs concentration and to calculate the reduction of the concentration of single masses and, finally, we will provide examples of the performances of a new implementation of this technique based on a time of flight (TOF) analyser. Instead of the usual quadrupole mass filter, the TOF provides an increase of analytical information and the possibility to separate important compounds that in the quadrupole version were not or only indirectly quantifiable. In conclusion we suggest that PTR-MS analysis can be a valuable tool for the rapid and on site monitoring of odour emission and plant operation.