Dynamic Headspace Gas Chromatography-mass Spectrometry Research Articles

Biopesticide Trunk Injection Into Apple Trees: A Proof of Concept for the Systemic Movement of Mint and Cinnamon Essential Oils.

The use of conventional pesticides is debated because of their multiple potential adverse effects on non-target organisms, human health, pest resistance development and environmental contaminations. In this setting, this study focused on developing alternatives, such as trunk-injected essential oil (EO)-based biopesticides. We analysed the ecophysiology of apple trees (Malus domestica) following the injection of Cinnamomum cassia and Mentha spicata nanoemulsions in the tree’s vascular system. Targeted and untargeted volatile organic compounds (VOCs) analyses were performed on leaf-contained and leaf-emitted VOCs and analysed through dynamic headspace–gas chromatography–mass spectrometry (DHS-GC-MS) and thermal desorption unit (TDU)-GC-MS. Our results showed that carvone, as a major constituent of the M. spicata EO, was contained in the leaves (mean concentrations ranging from 3.39 to 19.7 ng gDW–1) and emitted at a constant rate of approximately 0.2 ng gDW–1 h–1. Trans-cinnamaldehyde, C. cassia’s major component, accumulated in the leaves (mean concentrations of 83.46 and 350.54 ng gDW–1) without being emitted. Furthermore, our results highlighted the increase in various VOCs following EO injection, both in terms of leaf-contained VOCs, such as methyl salicylate, and in terms of leaf-emitted VOCs, such as caryophyllene. Principal component analysis (PCA) highlighted differences in terms of VOC profiles. In addition, an analysis of similarity (ANOSIM) and permutational multivariate analysis of variance (PERMANOVA) revealed that the VOC profiles were significantly impacted by the treatment. Maximum yields of photosystem II (Fv/Fm) were within the range of 0.80–0.85, indicating that the trees remained healthy throughout the experiment. Our targeted analysis demonstrated the systemic translocation of EOs through the plant’s vascular system. The untargeted analysis, on the other hand, highlighted the potential systemic acquired resistance (SAR) induction by these EOs. Lastly, C. cassia and M. spicata EOs did not appear phytotoxic to the treated trees, as demonstrated through chlorophyll fluorescence measurements. Hence, this work can be seen as a proof of concept for the use of trunk-injected EOs given the systemic translocation, increased production and release of biogenic VOCs (BVOCs) and absence of phytotoxicity. Further works should focus on the ecological impact of such treatments in orchards, as well as apple quality and production yields.

Determination of certain VOCs in paints and architectural coatings by dynamic headspace gas chromatography-mass spectrometry.

A quantitative method for the determination of the following VOCs: acetone, dichloromethane, dimethyl carbonate, methyl acetate, tertiary butyl acetate, chlorobenzotrifluoride (4-CBTF) and propylene carbonate in paints was developed in support of Environment and Climate Change Canada's Automotive Refinishing Product and Architectural Coatings VOC Concentration Limits regulations. These compounds are excluded from the VOC definition by Canadian Environmental Protection Act (CEPA) regulations, and their content do not contribute to the overall VOC content in products for regulatory purposes. The method is based on Dynamic Headspace GC-MS. It was determined that activated carbon is the best trapping medium for these compounds. The technique has been compared to a currently used direct injection technique, with comparable results. Contrary to the direct injection method which requires complex sample handling prior to injection in the gas chromatograph, the dynamic headspace method practically eliminates the need for sample handling allowing for much shorter sample turnover and reducing the possibility of sampling handling errors.

Methyl halide production by cultures of marine thraustochytrids, Aurantiochytrium sp., Botryochytrium radiatum, and Schizochytrium sp.

The oceans are an important source of the methyl halides released into the atmosphere and impacting the stratospheric ozone layer. Marine bacteria such as Erythrobacter and Pseudomonas are known to be sources of methyl halides in marine environments, but the production of methyl halides by thraustochytrids, the other decomposers in the marine ecosystem, have not been studied. Here, we report the productions of three methyl halides, CH3Cl, CH3Br, and CH3I, in cultures of thraustochytrids. Thraustochytrids were incubated at 20 °C, 25 °C, and 30 °C, and the concentrations of methyl halides in the gas phase above these cultures were determined using dynamic headspace gas chromatography–mass spectrometry. Growth of thraustochytrids was monitored by measuring optical density at 600 nm during the culture period. Cell density was also measured for some samples of thraustochytrids by counting with a plankton-counting chamber during the culture period. Three of the four tested strains of marine thraustochytrids were found to produce methyl halides in culture: Botryochytrium radiatum produced CH3Cl and CH3I while Aurantiochytrium sp. and Schizochytrium sp. produced CH3Br. Increases of CH3Cl, CH3Br, and CH3I concentrations were observed during the exponential-growth phase in all cultures of the three thraustochytrids, except for the 30 °C culture of B. radiatum. The maximum concentration for CH3Cl production by a thraustochytrid (B. radiatum) was increased as the culture temperature increased from 20 °C to 30 °C; the maximum concentrations of CH3Cl in the cultures incubated at 20 °C, 25 °C, and 30 °C were about 6000, 9600 and 14,000 pmol L−1, respectively. However, the maximum concentrations for the CH3I production of thraustochytrid (B. radiatum) decreased when the temperature was increased from 20 °C to 30 °C. To the best of our knowledge, this is the first report of methyl halide production by heterotrophic thraustochytrids. Our results suggest that thraustochytrids may be a source of methyl halides in marine environments.

Emission analysis of recycled tire rubber modified asphalt in hot and warm mix conditions.

The hazardous emissions of crumb rubber (CR) modified asphalt during construction has been a concern for a long period. This study aims to identify the emission components in the CR modified asphalt in traditional hot mix asphalt (HMA) and with recently developed warm mix asphalt (WMA). The dynamic headspace gas chromatography-mass spectrometry (GCMS) was employed for identifying the emission of asphalt binders at 120°C, 140°C and 160°C. The coupling of gas chromatography and Fourier-transform infrared spectroscopy (GC-FTIR) was used to analyze the emission during the plant mixing for conventional HMA, CR-HMA and CR-WMA. The results showed the emission amount was highly dependent on mixing temperature. The warm mix technology can reduce the emission level significantly and should be encouraged in the asphalt mixture containing CR. Asphalt source and other extra additives in producing CR modified asphalt can also affect the emission significantly. Asphalt mixture containing CR can release toxic emissions such as xylene and toluene significantly higher compared to that without CR. In addition, it was found that the emission amount from the GCMS test for asphalt binder was lower than that in the field test for asphalt mix due to the thin asphalt film of asphalt mix.

Effect of temperature on the production rates of methyl halides in cultures of marine proteobacteria

Abstract Methyl halides released from the ocean serve as important carriers of halogen into the atmosphere. The transported halogens are released into the atmosphere through photolysis, and catalyze ozone depletion. Marine bacteria are known to be a source of methyl halides in marine environments, but the effects of environmental temperature on the production of methyl halides by bacteria have not been studied. Here, we examined the effect of temperature on methyl halide production in a culture of marine bacteria (HKF-1) belonging to Erythrobacter , which was incubated for several days at 15 °C, 20 °C, 25 °C, or 30 °C. We also analyzed the effect of temperature on the production of methyl halides in a culture of the marine γ -proteobacterium Pseudomonas stutzeri . The concentrations of methyl halides such as CH 3 Cl, CH 3 Br, and CH 3 I in the gas phase above cultured samples were determined using dynamic headspace gas chromatography–mass spectrometry. Bacterial growth was monitored by measuring the optical density at 600 nm. The production rate of CH 3 Cl by marine bacteria (HKF-1) was increased with increasing temperature from 15 °C to 30 °C, and the maximum production rate for CH 3 Cl was ~ 19 pmol (10 9 cells) − 1 d − 1 at 30 °C, which was about 26 times higher than that at 15 °C (~ 0.7 pmol (10 9 cells) − 1 d − 1 ). The production rates of CH 3 Cl by P. stutzeri were also increased with increasing temperature from 15 °C to 30 °C. The production rates for CH 3 Br by bacteria (HKF-1) were increased with increasing temperature from 15 °C to 30 °C, whereas changes in the production rates for CH 3 I by these two bacteria were relatively small during the temperature rise from 15 °C to 30 °C. Higher production rates of CH 3 Cl, CH 3 Br, and CH 3 I were observed during the exponential phase than during the stationary phase in the cultures of HKF-1. The ratio of production rates (CH 3 Cl:CH 3 Br:CH 3 I) was 1.0:0.12:0.015 in the cultures of HKF-1, and this ratio was almost constant between 15 °C and 25 °C. These results suggested that water temperature could affect the production of methyl halides derived from bacteria and would be a significant factor for estimating the emissions of methyl halides from marine environments.

Effect of Fermentation Temperature on the Volatile Composition of Kimchi.

This study was conducted to evaluate the effect of fermentation temperature on the volatile composition in Kimchi. Kimchi was fermented at 2 temperature conditions (4 and 20 °C). Volatile compounds of Kimchi samples were analyzed during the fermentation periods using the dynamic headspace gas chromatography-mass spectrometry method. The optimum ripening time for the Kimchi fermented at 4 °C was 35 d, and that of 20 °C was 2 d. The pH at the optimum ripening time was 4.97 and 4.41, and the titratable acidity was 0.59% and 0.76% for the Kimchi fermented at 4 and 20 °C, respectively. Forty different types of volatile compounds, including alcohol, aldehyde, ester, and sulfur compounds, were identified. The Kimchi fermented at 20 °C produced greater amounts of volatile compounds than that at 4 °C. The amounts of most volatiles increased as the fermentation time increased, but those of aldehydes decreased rapidly during both 4 and 20 °C fermentation. Organic acids, ester, and nitriles were detected only in Kimchi fermented at 20 °C. The amounts of dimethyl disulfide, methyl-2-propenyl disulfide, and di-2-propenyl disulfide produced from the Kimchi fermented at 20 °C were more than 2-times of those at 4 °C. Therefore, it is concluded that the strong pungent odor of Kimchi fermented at 20° C is probably due to the high amount of organic acids (low pH) and sulfur compounds (dimethyl disulfide, methyl-2-propenyl disulfide, and di-2-propenyl disulfide) between the 2 Kimchi.

Quantitative Analysis of Bioactive Compounds from Aromatic Plants by Means of Dynamic Headspace Extraction and Multiple Headspace Extraction-Gas Chromatography-Mass Spectrometry.

Seven monoterpenes in 4 aromatic plants (sage, cardamom, lavender, and rosemary) were quantified in liquid extracts and directly in solid samples by means of dynamic headspace-gas chromatography-mass spectrometry (DHS-GC-MS) and multiple headspace extraction-gas chromatography-mass spectrometry (MHSE), respectively. The monoterpenes were 1st extracted by means of supercritical fluid extraction (SFE) and analyzed by an optimized DHS-GC-MS. The optimization of the dynamic extraction step and the desorption/cryo-focusing step were tackled independently by experimental design assays. The best working conditions were set at 30 °C for the incubation temperature, 5 min of incubation time, and 40 mL of purge volume for the dynamic extraction step of these bioactive molecules. The conditions of the desorption/cryo-trapping step from the Tenax TA trap were set at follows: the temperature was increased from 30 to 300 °C at 150 °C/min, although the cryo-trapping was maintained at -70 °C. In order to estimate the efficiency of the SFE process, the analysis of monoterpenes in the 4 aromatic plants was directly carried out by means of MHSE because it did not require any sample preparation. Good linearity (r2) > 0.99) and reproducibility (relative standard deviation % <12) was obtained for solid and liquid quantification approaches, in the ranges of 0.5 to 200 ng and 10 to 500 ng/mL, respectively. The developed methods were applied to analyze the concentration of 7 monoterpenes in aromatic plants obtaining concentrations in the range of 2 to 6000 ng/g and 0.25 to 110 μg/mg, respectively.

Development of a dynamic headspace gas chromatography–mass spectrometry method for on-site analysis of sulfur mustard degradation products in sediments

Sampling teams performing work at sea in areas where chemical munitions may have been dumped require rapid and reliable analytical methods for verifying sulfur mustard leakage from suspected objects. Here we present such an on-site analysis method based on dynamic headspace GC–MS for analysis of five cyclic sulfur mustard degradation products that have previously been detected in sediments from chemical weapon dumping sites: 1,4-oxathiane, 1,3-dithiolane, 1,4-dithiane, 1,4,5-oxadithiephane, and 1,2,5-trithiephane. An experimental design involving authentic Baltic Sea sediments spiked with the target analytes was used to develop an optimized protocol for sample preparation, headspace extraction and analysis that afforded recoveries of up to 60–90%. The optimized method needs no organic solvents, uses only two grams of sediment on a dry weight basis and involves a unique sample presentation whereby sediment is spread uniformly as a thin layer inside the walls of a glass headspace vial. The method showed good linearity for analyte concentrations of 5–200ng/g dw, good repeatability, and acceptable carry-over. The method's limits of detection for spiked sediment samples ranged from 2.5 to 11μg/kg dw, with matrix interference being the main limiting factor. The instrumental detection limits were one to two orders of magnitude lower. Full-scan GC–MS analysis enabled the use of automated mass spectral deconvolution for rapid identification of target analytes. Using this approach, analytes could be identified in spiked sediment samples at concentrations down to 13–65μg/kg dw. On-site validation experiments conducted aboard the research vessel R/V Oceania demonstrated the method's practical applicability, enabling the successful identification of four cyclic sulfur mustard degradation products at concentrations of 15–308μg/kg in sediments immediately after being collected near a wreck at the Bornholm Deep dumpsite in the Baltic Sea.

Decomposition of brominated organic halogens by cultures of marine proteobacteria: Phaeobacter, Roseobacter, and Rhodobacter

Brominated organic halogens such as bromoform (CHBr3) and dibromomethane (CH2Br2) play important roles as carriers of bromine from the ocean to the atmosphere. The bromine carried by these brominated methanes is released into the atmosphere, where it catalyzes ozone depletion. Previously, however, no microbial organisms capable of CHBr3 decomposition have been found in marine environments. In this study, we investigated bacteria to assess their capacity to decompose CHBr3 in temperate oceans. Bacteria were incubated with 13CHBr3 at 25°C and the concentrations of trace gases in the gas phase above the cultured samples were determined using dynamic headspace gas chromatography–mass spectrometry. Bacterial growth was monitored by measuring the optical density at 600 nm. 13CHBr3 was decomposed for several days by cultures of three different bacteria, Phaeobacter gallaeciensis, Roseobacter denitrificans, and Rhodobacter vinaykumarii, suggesting temperate marine bacteria can decompose CHBr3. The maximum 13CHBr3 decomposition rate was observed in the culture of P. gallaeciensis. The half-lives for 13CHBr3 decomposition by P. gallaeciensis, R. denitrificans, and R. vinaykumarii were 0.4 (0.3–0.5), 2.7 (2.5–2.9), and 2.0 (1.9–2.0) days, respectively. 13CH2Br2 and 13CHBr2Cl production were observed in the cultures, suggesting that 13CHBr3 was transformed into these compounds, and the production ratio of 13CH2Br2 was approximately 30% of the amount of 13CHBr3 spiked into the bacterial cultures. In contrast to CHBr3, CH2Br2 was not decomposed by the P. gallaeciensis, R. denitrificans, and R. vinaykumarii cultures. These results suggest that aquatic bacteria could act as a new sink for CHBr3 through decomposition in marine environments.

A comparative study on aromatic profiles of strawberry vinegars obtained using different conditions in the production process

Impact odorants in strawberry vinegars produced in different containers (glass, oak and cherry barrels) were determined by gas chromatography–olfactometry using modified frequency (MF) technique, and dynamic headspace gas chromatography–mass spectrometry. Aromatic profile of vinegar from strawberry cooked must was also studied. All strawberry vinegars retained certain impact odorants from strawberries: 3-nonen-2-one, (E,E)-2,4-decadienal, guaiacol, nerolidol, pantolactone+furaneol, eugenol, γ-dodecalactone and phenylacetic acid. Isovaleric acid, pantolactone+furaneol, p-vinylguaiacol, phenylacetic acid and vanillin were the most important aroma-active compounds in all vinegars. The strawberry cooked must vinegar accounted for the highest number of impact odorants. Wood barrels provided more aroma complexity than glass containers. Impact odorants with grassy characteristics were predominant in vinegar from glass containers, and those with sweet and fruity characteristics in vinegars from wood barrels. Principal component analysis indicated that the production process led to differences in the impact odorants.

Impact of starter cultures and fermentation techniques on the volatile aroma and sensory profile of chocolate

The sensory quality of chocolate is widely determined by the qualitative and quantitative composition of volatile compounds resulting from microbial metabolism during fermentation, and Maillard reactions taking place during drying, roasting and conching. The influence of applying mixed starter cultures on the formation of flavour precursors, composition of volatile aroma compounds and sensory profile was investigated in cocoa inoculated with cultures encompassing a highly aromatic strain of Pichia kluyveri or a pectinolytic strain of Kluyveromyces marxianus, and compared to commercially fermented heap and tray cocoa. Although only minor differences in the concentration of free amino acids and reducing sugars was measured, identification and quantification by dynamic headspace gas chromatography–mass spectrometry (HS/GC–MS) revealed pronounced differences in the composition of volatiles in roasted cocoa liquors and finished chocolates. 19 of the 56 volatile compounds identified in the chocolates were found in significantly higher amounts in the tray fermented sample, whilst significantly higher amounts of 2-methoxyphenol was measured in the two inoculated chocolates. The P. kluyveri inoculated chocolate was characterized by a significantly higher concentration of phenylacetaldehyde and the K. marxianus inoculated chocolate by significantly higher amounts of benzyl alcohol, phenethyl alcohol, benzyl acetate and phenethyl acetate compared to a spontaneously fermented control. Sensory profiling described the heap and tray fermented chocolates as sweet with cocoa and caramel flavours, whilst the inoculated chocolates were characterized as fruity, acid and bitter with berry, yoghurt and balsamic flavours. The choice of fermentation technique had the greatest overall impact on the volatile aroma and sensory profile, but whilst the application of starter cultures did affect the volatile aroma profile, differences were too small to significantly change consumer perception of the chocolates as compared to a spontaneously fermented control.

Volatile component profiles of conventional and lactose-hydrolyzed UHT milk—a dynamic headspace gas chromatography-mass spectrometry study

Lactose-hydrolyzed milk gains still increasing market share, and understanding the chemical characteristics of lactose-hydrolyzed milk products is important for the dairy industry. The aim of the present study was to identify and compare volatile compounds of commercial lactose-hydrolyzed and conventional ultra-high temperature (UHT) milk. For this purpose, the volatile compounds of lactose-hydrolyzed (<1% lactose), conventional (100% lactose), and filtered (60% lactose) UHT-treated milk were extracted using dynamic headspace sampling and analyzed by gas chromatography-mass spectrometry (GC-MS). A total of 24 volatile compounds were identified including ketones, aldehydes, and sulfides. Overall, principal component analysis (PCA) showed grouping of the different milk types, with loadings indicating a higher concentration of ketones in conventional versus lactose-hydrolyzed UHT milk, but PCA also indicated a marked batch-to-batch variation. Elucidation of individual volatile compounds detected also revealed that the content of ketones in general was higher in conventional UHT milk than in lactose-hydrolyzed milk; however, no significant differences in the volatile compound profiles could be identified between the various milk types as a result of the batch-to-batch variation. The present study highlights a useful analytical method based on dynamic headspace sampling and GC-MS to profile volatiles important for the flavor characteristics of lactose-hydrolyzed and conventional UHT milk. In addition, the present study reveals that a considerable batch-to-batch variation exists in industrially produced batches of lactose-hydrolyzed UHT milk, which must be considered an important challenge for the dairy industry.

Impact of processing steps on the composition of volatile compounds in cheese powders

Changes in the composition of volatile compounds during processing of cheese powders, made from Emmental and Danbo cheese were analysed by dynamic headspace gas chromatography–mass spectrometry. Samples comprised cheese, melted cheese slurry, the slurry heat treated using three different time and temperature combinations, and the spray‐dried cheese powder. About 100 volatile compounds were identified. During melting of the cheese the level of some volatile compounds increased significantly; heat treatment mainly leads to a loss of compounds and spray drying leads to a substantial reduction of volatile compounds, with the exception of a range of aldehydes that increased. The final cheese powders could, however, be distinguished according to cheese type.

Oxidative stability and sensory quality of meat from broiler chickens fed a bacterial meal produced on natural gas

Bacterial meal (BPM) produced from bacteria grown on natural gas is a feed source containing approximately 70% CP and 10% lipids with predominantly C16:0 and C16:1 fatty acids. The effect of increasing dietary levels (0, 40, 80, or 120 g/kg) of BPM on fatty acid composition, the profile of volatiles by dynamic headspace gas chromatography-mass spectrometry, and sensory quality of frozen-stored broiler chicken thigh meat was examined. Increasing levels of BPM increased (linear, P < 0.0001) the content of saturated fatty acids, tended (linear, P = 0.05) to increase the content of monounsaturated fatty acids, and tended (linear, P = 0.08) to decrease the content of polyunsaturated fatty acids in the meat. Feeding BPM reduced (linear, P ≤ 0.03) levels of the volatile lipid oxidation products butanal, hexanal, heptanal, and nonanal in the meat during frozen storage but had no significant effects on the sensory quality parameters related to odor and flavor. The presence of antioxidants in BPM may have reduced lipid oxidation in the meat. To conclude, adding BPM to diets reduced the formation of volatile lipid oxidation products during frozen storage of the broiler thigh meat. Dynamic headspace gas chromatography-mass spectrometry was a more sensitive method in detecting early lipid oxidation compared with TBA reactive substances and sensory quality analyses in broiler thigh meat.

Is flower scent influencing host plant selection of leaf-galling sawflies (Hymenoptera, Tenthredinidae) on willows?

Though it is known that flower scent not only attracts pollinators but also herbivores, little is known about the importance of flower scent on the distribution of leaf herbivores among individuals within a plant species. In this study we determined the distribution of galls induced by the sawfly Pontania proxima (Serville 1823) (Hymenoptera, Tenthredinidae, Nematinae) on flowering and non-flowering representatives of several clones belonging to Salix fragilis and S. × rubens (Salicaceae). Further, amounts and composition of scent of flowering and non-flowering twigs were compared (dynamic headspace-gas chromatography–mass spectrometry, DHS-GC–MS), and a scent sample collected from flowering twigs of S. fragilis was tested by coupled gas chromatography and electroantennographic detection (GC-EAD) on the antennae of P. proxima females. The results show that the presence of flower catkins on plants led to a higher degree of allocation with galls, but the number of galls differed not between flowering and non-flowering plants. The DHS-GC–MS analyses revealed that the total amount of flower scent emitted per flowering twig is about 90 times higher than the scent emitted by a non-flowering twig. Further, several compounds were emitted only by flowering but not by non-flowering twigs. In the GC-EAD analyses, antennae consistently responded not only to green leaf volatiles, but also to compounds emitted only by the flowers (e.g. 1,4-dimethoxybenzene). These flower scent compounds are suggested to affect the host plant choice by attracting more sawflies from the distance to flowering plants compared to non-flowering plants. The EAD-active compounds emitted from vegetative plant parts are assumed to act as long-distance signals especially when flowers are absent on host plants, e.g. during the oviposition period of the second generation of P. proxima.

Influence of chemical composition of olive oil on the development of volatile compounds during frying

In this study, 15 virgin olive oils from an industrial oil plant in the Abruzzo region were analyzed in terms of the volatile compounds responsible for the characteristic odor and olfactory perception of virgin olive oils and its modification upon frying (up to 60 min of heat treatment). Dynamic headspace–gas chromatography–mass spectrometry analysis was used to evaluate the volatile profile before and after each frying step and examine correlations with qualitative characteristic of oil (fatty acid composition, total phenolic compound content, tocopherols and pigments). The chemometric approach (genetic algorithms–partial least squares/multiple linear regression) developed for this study is a novel model for data treatment to select important variables in olive oil composition and understand their influence on spoilage during frying. An inverse correlation between oleic acid content and formation of toxic volatiles such as acrolein and crotonal during frying was demonstrated. Moreover, it was also observed that pigments such as chlorophylls, pheophytins, and carotenoids may prevent the formation of some aldehydes during frying.

Discrimination of pasture-fed lambs from lambs fed dehydrated alfalfa indoors using different compounds measured in the fat, meat and plasma

The last decade has seen important developments in the use of carotenoid pigments to authenticate pasture-feeding in ruminants. However, dehydrated alfalfa is sometimes incorporated in grain-based concentrates fed to stall-raised lambs, which may affect the reliability of the pasture-feeding authentication methods based on carotenoids in plasma and fat, due to significant residual carotenoid levels post-dehydration. The aim of this study was to examine whether other compounds can give additional information to authenticate diet and discriminate pasture-fed lambs from lambs fed high levels of alfalfa indoors. Two feeding treatments were compared: pasture-feeding (P) v. stall-feeding with dehydrated alfalfa (A). Each treatment group consisted of seven male Romanov × Berrichon lambs. Pasture-fed (P) lambs grazed a permanent graminaceae-rich pasture maintained at a leafy, green stage, offered ad libitum; they received no supplementation at pasture. A-group lambs were individually penned and fed dehydrated alfalfa and straw; their feed level was adjusted to achieve a similar growth pattern as for P-group lambs. Plasma carotenoid concentration was measured at slaughter by spectrophotometry. The reflectance spectrum of perirenal and subcutaneous caudal fat was measured at 24-h post mortem and used to calculate an index (absolute value of the mean integral (AVMI)) quantifying light absorption by carotenoid pigments present in the fat. The nitrogen (N) stable isotopes ratio (δ15N) in both feed and longissimus dorsi muscle was measured by isotopes ratio mass spectrometry (IRMS). Volatile compounds were analyzed in perirenal fat for five randomly chosen lambs per treatment, using dynamic headspace–gas chromatography–mass spectrometry. Plasma carotenoid concentration and AVMI of the fat did not differ significantly between P- and A-group lambs, but there were significant between-treatment differences in meat δ15N values and in the terpene profiles of perirenal fat. A discriminant analysis performed using three compounds in different animal tissues (δ-cadinene in perirenal fat, δ15N value of the meat and plasma carotenoid concentration) clearly separated pasture-fed lambs from lambs fed high levels of alfalfa indoors.

Authentication of Meat Products: Determination of Animal Feeding by Parallel GC-MS Analysis of Three Adipose Tissues

Authentication of farm animal rearing conditions, especially the type of feeding, is a key issue in certification of meat quality and meat products. The purpose of this article was to analyze in parallel the volatile fraction of three adipose tissues excised from 16 lambs in order to authenticate two animal diets: pasture (n = 8) and concentrate (n = 8). On the basis of growth rate and anatomical location, three different lamb adipose tissues were analyzed: perirenal fat (PRF), caudal subcutaneous fat (CSCF), and heart fat (HF). An initial experiment was used to optimize the extraction of volatile compounds from the adipose tissues. Using a lipid liquid phase extraction, heating the ground tissue to 70 degrees C, was shown to be the best sample preparation mode before dynamic headspace-gas chromatography-mass spectrometry (DH-GC-MS) analysis to achieve a good representation of the starting material, while getting a good extraction and reproducibility. Next, the application of an instrumental drifts correction procedure to DH-GC-MS data enabled the identification of 130 volatile compounds that discriminate the two diets in one or several of the three tissues: 104 were found in PRF, 75 in CSCF, and 70 in HF. Forty-eight of these diet tracers, including 2,3-octanedione, toluene, terpenes, alkanes, alkenes, and ketones, had previously been identified as ruminant pasture-diet tracers and can be considered generic of this type of animal feeding. Moreover, 49 of the 130 compounds could identify diets in only one tissue, suggesting that complementary analysis of several tissues is superior for diet identification. Finally, multivariate discriminant analyses confirmed that the discrimination was improved when PRF, CSCF, and HF were considered simultaneously, even if HF contributed minimal information.

Differentiation of the volatile profile of microbiologically contaminated canned tomatoes by dynamic headspace extraction followed by gas chromatography–mass spectrometry analysis

The aromatic profile of microbiologically contaminated canned tomatoes was analyzed by the dynamic headspace extraction technique coupled with gas chromatography–mass spectrometry. Canned tomatoes contaminated with Escherichia coli, Saccharomyces cerevisiae and Aspergillus carbonarius were analyzed after 2 and 7 days. About 100 volatiles were detected, among which alcohols, aldehydes and ketones were the most abundant compounds. Gas chromatographic peak areas were used for statistical purposes. First, principal component analysis was carried out in order to visualize data trends and clusters. Then, linear discriminant analysis was performed in order to detect the set of volatile compounds ables to differentiate groups of analyzed samples. Five volatile compounds, i.e. ethanol, β-myrcene, o-methyl styrene, 6-methyl-5-hepten-2-ol and 1-octanol, were found to be able to better discriminate between uncontaminated and contaminated samples. Prediction ability of the calculated model was estimated to be 100% by the “leave-one-out” cross-validation. An electronic nose device was then used to analyze the same contaminated and not contaminated canned tomato samples. Preliminary results were compared with those obtained by dynamic headspace gas chromatography–mass spectrometry, showing a good agreement.

Determination of volatile compounds in San Daniele ham using headspace GC–MS

The volatile fraction of San Daniele hams was evaluated in barrows and gilts belonging to two commercial breeds. A group of 120 pigs, reared under the same conditions, were slaughtered, and the right ham seasoned/cured for 12 months, in accordance with the San Daniele Consortium protocol. At the end of ripening, 16 hams (four of each gender and breed) were selected and analysed for volatile composition, using a dynamic headspace gas chromatography-mass spectrometry (DHS–GC–MS) technique. Seventy five compounds belonging to eight different chemical groups were identified in the hams. Alcohols were the most abundant constituents (41.38%) followed by aldehydes (31.53%). The possibility of classifying hams according breed and gender, using volatile compounds as independent variables, was analysed by principal component analysis, alcohols were the most suitable compounds to discriminate hams. Data from a larger number of samples are required to validate the conclusions.