Application of Fourier-Transform Infrared Spectroscopy for the Assessment of Wine Spoilage Indicators: A Feasibility Study.

Wine aroma is one of the most frequently used and explored quality indicators. Typically, its assessment involves estimating the volatile composition of wine or highly trained assessors conducting sensory analysis. However, current methodologies rely on slow, expensive and complicated analytical procedures. Additionally, sensory evaluation is inherently subjective in nature. Therefore, the aim of this work is to verify the feasibility of using FTIR spectroscopy as a fast and easy methodology for the early detection of some of the most common off-odors in wines. FTIR spectroscopy was combined with partial least squares (PLS) regression for the simultaneous measurement of isoamyl alcohol, isobutanol, 1-hexanol, butyric acid, isobutyric acid, decanoic acid, ethyl acetate, furfural and acetoin. The precision and accuracy of developed calibration models (R2P > 0.90, range error ratio > 12.1 and RPD > 3.1) proved the ability of the proposed methodology to quantify the aforementioned compounds.

Genotypic and phenotypic characterization of the food spoilage bacterium Brochothrix thermosphacta.

Microbial food spoilage is responsible for significant economic losses. Brochothrix thermosphacta is one of the major bacteria involved in the spoilage of meat and seafood. Its growth and metabolic activities during food storage result in the production of metabolites associated with off-odors. In this study, we evaluated the genotypic and phenotypic diversity of this species. A collection of 161 B. thermosphacta strains isolated from different foods, spoiled or not, and from a slaughterhouse environment was constituted from various laboratory collections and completed with new isolates. A PCR test based on the rpoB gene was developed for a fast screening of B. thermosphacta isolates. Strains were typed by MALDI-TOF MS, rep-PCR, and PFGE. Each typing method separated strains into distinct groups, revealing significant intra-species diversity. These classifications did not correlate with the ecological origin of strains. The ability to produce acetoin and diacetyl, two molecules associated with B. thermosphacta spoilage, was evaluated in meat and shrimp juices. The production level was variable between strains and the spoilage ability on meat or shrimp juice did not correlate with the substrate origin of strains. Although the B. thermosphacta species encompasses ubiquitous strains, spoiling ability is both strain- and environment-dependent.

Assessment of Melt Compounding with Zeolites as an Effective Deodorization Strategy for Mixed Plastic Wastes and Comparison with Degassing.

The emission of off-odors from mechanically recycled plastics severely limits their re-introduction into the market for the production of new objects, for the same use or even for less demanding applications, thus hindering the implementation of an effective circular economy for plastics. The addition of adsorbing agents during the extrusion of polymers represents one of the most promising strategy to reduce the odorous emissions of plastics, due to its characteristics of cost-effectiveness, flexibility and low energy consumption. The novelty of this work lies in the assessment of zeolites as VOC adsorbents during the extrusion of recycled plastics. They appear more suitable than other types of adsorbents, due to their ability to capture and "hold" the adsorbed substances at the high temperatures of the extrusion process. Moreover, the effectiveness of this deodorization strategy was compared with the traditional degassing technique. Two types of mixed polyolefin wastes, coming from completely different collection and recycling processes, were tested: Fil-S (Film-Small), deriving from post-consumer flexible films of small size, and PW (pulper waste), which is the residual plastic waste obtained from the paper recycling process. The melt compounding of the recycled materials with two micrometric zeolites (zeolite 13X and Z310) resulted as more effective in the off-odors removal with respect to degassing. In particular, the highest reduction (-45%) of the Average Odor Intensity (AOI) was measured for both PW/Z310 and Fil-S/13X systems at 4 wt% of the zeolites' amount, compared with the corresponding untreated recyclates. Finally, by combining degassing and melt compounding with zeolites, the best result was obtained for the composite Fil-S/13X, whose Average Odor Intensity resulted as quite close (+22%) to the one of the virgin LDPE.

Myosin head as the main off-odors binding region: Key binding residues and conformational changes in the binding process.

This study aims to elucidate the dynamic binding characteristics between off-odors (hexanal, 1-octen-3-ol, nonanal) and myosin at cold storage (277 K) and oral temperatures (310 K) through spatial-temporal molecular dynamics (MD) simulation. Conformational analysis indicated that binding with off-odors could not significantly change the myosin secondary structure, and the myosin/(off-odors) structure became a stable and compact state in the later binding stages. Myosin head was the primary binding region with hydrophobic interactions as the dominant force rather than hydrogen bonds (average bond number 202.62 vs 55.20). Furthermore, the myosin/(off-odors) had larger binding energy at 310 than 277 K, and the myosin-nonanal showed the highest binding strength of 4050.93 kJ/mol at 310 K. The binding sites were observed to be concentrated in the 180-249, 350-410, 800-950 amino acid regions of myosin head, especially, Lys185, Tyr347, Leu901. These results provide accurate linkages between off-odors and myosin, laying a theoretical foundation for deodorization of fish products.

A method for the quantitative and reversible trapping of sulfidic gases from headspaces and its application to the study of wine reductive off-odors.

Some relevant food systems release tiny amounts of sulfidic gases, whose measurement is difficult because of their inherent instability. The present paper demonstrates that Cu(I) solutions trap quantitatively and stabilize sulfidic gases. Once trapped, the gases remain stable for weeks at 4 °C and at least 8 days at 75 °C. Trapped gases can be quantitatively released with tris(2-carboxyethyl) phosphine (TCEP) and brine dilution and then determined by GC. Trapping solutions, placed in 20-mL opened vials housed in 100 mL hermetically-sealed flasks containing wine in anoxia, have been used to monitor the release of sulfidic gases by wines, revealing that at 50 °C, up to 400 µg/L of H2S and 58 µg/L of MeSH can be released in 68 days, and 3-5 times more at 75 °C in 28 days. The possibility to differentiate between released and accumulated amounts provides key clues to understanding the fate of sulfidic gases in wine and other food systems.

Accurate quantitative determination of the total amounts of Strecker aldehydes contained in wine. Assessment of their presence in table wines.

Strecker aldehydes (SAs) are key determinants of wine shelf-life and can be present in unoxidized wines in odorless forms, such as hydroxyalkylsulfonates, imines or acetals. A robust and accurate method for the determination of total forms of SAs, based on the classical derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and in the selective solid phase extraction of derivatives has been optimized and validated. Matrix effects have been solved by the use of adequate internal standards and by large-enough equilibration times under anoxic conditions. Method figures of merit are highly satisfactory in terms of detection limits (<0.1 µg/L), linearity (R2 > 0.997), reproducibility (5-13%) and recoveries (RSDs, between 2 and 10%, for 3-methylbutanal, 14%). The analysis of total SAs in 108 Spanish wines revealed that between 52% and 70% of unoxidized red wines and likely a similar fraction of white wines, contain levels of SAs high enough to cause oxidative aromas if bound forms of SAs cleave.

Hydrophobic bonds-dominated key off-odors/silver carp myofibrillar protein interactions, and their binding characteristics at cold storage and oral temperatures.

This study revealed the interaction mechanism between silver carp myofibrillar protein (MP) and key off-odors by combining fluorescence spectroscopy with molecular dynamics (MD) simulation. Spectroscopic results exhibited a dynamic quenching mechanism between MP and off-odors. Thermodynamic analysis indicated that the MP/off-odors interaction was spontaneous (ΔG° < 0) and dominated by hydrophobic interactions (ΔH° > 0, ΔS° > 0). Meanwhile, the binding affinity was in the order of nonanal (n = 1.38) > hexanal (n = 0.89) > 1-octen-3-ol (n = 0.65), which was further verified by the MD results. Among off-odors, nonanal had the highest binding energy with myosin (8105.66 kJ/mol) and formed more hydrophobic binding sites to Trp residues in myosin head (e.g., Trp820 and Trp822), thereby changing myosin conformations via both physical and chemical interactions. Additionally, higher binding energies of myosin/off-odors were observed at oral temperature (37 °C) than at cold storage temperature (4 °C), implying that less off-odors were released at 37 °C.

The Exploitation of a Hempseed Byproduct to Produce Flavorings and Healthy Food Ingredients by a Fermentation Process.

Following the One Health principles in food science, the challenge to valorize byproducts from the industrial sector is open. Hemp (Cannabis sativa subsp. sativa) is considered an important icon of sustainability and as an alternative food source. Hemp seed bran, in particular, is a byproduct of industrial hemp seed processing, which is not yet valorized. The success, and a wider market diffusion of hemp seed for food applications, is hindered by its unpleasant taste, which is produced by certain compounds that generally overwhelm the pleasant bouquet of the fresh product. This research concerns the exploration of hemp seed bran through fermentation using beneficial lactobacilli, focusing on the sensorial and bioactive traits of the products when they are subjected to bacterial transformation. By studying of the aromatic profile formation during the fermentation process the aim was to modulate it in order to reduce off-odors without affecting the presence of healthy volatile organic compounds (VOCs). Applying multivariate analyses, it was possible to target the contribution of processing parameters to the generation of flavoring and bioactive compounds. To conclude, the fermentation process proposed was able to reduce unpleasant VOCs, whilst at the same time keeping the healthy ones, and it also improved nutritional quality, depending on time and bacterial starters. The fermentation proposed was a sustainable biotechnological approach that fitted perfectly with the valorization of hemp byproducts from the perspective of a green-oriented industrial process that avoids synthetic masking agents.

Importance of profile of volatile and off-odors compounds from different recycled polypropylene used for food applications.

Nowadays, polypropylene is one of the most common polymers used in the food packaging industry due to its good functionality and relatively low cost. Nevertheless, usage of plastic disposable packaging can be a generator of plastic pollution having negative environmental effects. A feasible solution for this issue would be to recycle. The polypropylene samples were submitted to two processes, forced contamination, and recycling, and they were analyzed by solid-phase microextraction gas chromatograph-olfactometry-mass spectrometry. 45 different volatile compounds were identified and 9 of them presented distinct odoriferous activities. Among them, two important markers were detected: diethyl phthalate (probably coming from the catalyst of PP polymerization, intentionally added substance (IAS)), and glycerine (a marker of non-intentionally added substances (NIAS)).

Gas chromatographic-sulfur chemiluminescent detector procedures for the simultaneous determination of free forms of volatile sulfur compounds including sulfur dioxide and for the determination of their metal-complexed forms.

Three different procedures for the quantitative assessment of free and metal complexed volatile sulfur compounds (VSCs) and for the determination of truly free SO2 have been developed, taking advantage of a GC-sulfur chemiluminescent detector system (GC-SCD) with cryotrapping. The inertness of the inlet systems, together with the column used (SPB-1 sulfur) makes it possible to obtain a non-saturated perfectly Gaussian peak for SO2, well resolved from H2S. In the main procedure, the injection of 1 mL of the headspace of a sample prepared in complete anoxia and equilibrated at 30 °C makes it possible to get highly sensitive signals for all VSCs and free SO2. Detection limits are 3, 35 and 60 ng/L for H2S, MeSH and EtSH, 13 µg/L for truly free SO2 (at pH = 3.4, or 0.46 µg/L for molecular SO2), and better than 1 µg/L for other relevant sulfur volatiles. Method precision is also satisfactory and linearity covers the whole range of occurrence of these compounds. A second procedure, not making use of the cryotrapping unit, gives also satisfactory results, although with higher detection limits (0.03, 0.25 and 0.37 µg/L for free H2S, MeSH and EtSH, respectively). For the analysis of free plus metal-complexed forms, it has been demonstrated that the headspace injection of the vapors on a 1:10 brine dilution of the sample heated at 70 °C for 25 min, gives good estimates of the free + metal-complexed forms of H2S and wine mercaptans.

Determination of volatile compounds and their sensory impact in a biopolymer based on polylactic acid (PLA) and polyester.

Polylactic acid (PLA) is one of the most commonly used biopolymers for manufacturing food packaging; its control is very important to ensure consumers' health. In this work, a blend of PLA and polyester was studied and its volatile composition in the polymer and in the migration to food simulants was determined by gas chromatography-mass spectrometry (GC-MS) and atmospheric pressure gas chromatography-quadrupole-time of flight mass spectrometry (APGC-QTOF). The results showed that both techniques provided complementary information, to give complete information on the biopolymer's composition. Some compounds such as lactide or cyclopentanone were detected only by GC-MS while others, such as the cyclic dimer [AA-BD]2 (AA:adipic acid, BD:butanediol), were detected only by APGC-MS. In migration, lactide, AA-BD and [AA-BD]2 were identified in ethanol 95%. A GC-olfactometry study was also carried out. Some compounds showed sensory impact on the polymer odor but not in migration.

Elusive Chemistry of Hydrogen Sulfide and Mercaptans in Wine.

This paper summarizes, discusses, and complements recent findings about the fate of H2S and methanethiol (MeSH) during wine storage. Analytical assays to determine free volatile sulfur compounds (VSCs) and brine-releasable (BR-) VSCs in combination with accelerated reductive (AR) aging and micro-oxygenation (MOX) assays allow characterizing the different categories of species able to produce H2S and MeSH and the processes of interconversion. Each wine seems to contain a specific total amount of H2S and MeSH distributed into free, metal-complexed, and oxidized forms (di and polysulfides) interconnected through reversible redox equilibria whose external expression is wine redox potential. Oxidation transforms all mercaptans likely into nonvolatile disulfides and hydrodisulfides. In anoxia, these molecules are spontaneously and quantitatively reduced back. The concomitant accumulation of major wine thiols would provoke complex dissociation and the release of free H2S and MeSH. Additionally, total amounts can increase due to the metal-catalyzed desulfhydration of cysteine and methionine.

Effects of market type and time of purchase on oxidative status and descriptive off-odors and off-flavors of beef in Vietnam.

The objective of the current study was to determine the effects of market type (super market - SM, indoor market - IM, open market - OM) and sampling time (at the opening - T0 and 4 h after the opening - T4) on antioxidant capacity, lipid oxidation, and descriptive sensory attributes of beef in Vietnam. Values of FC and TEAC were greater in OM beef than IM and SM (P < 0.001) and FC value was also greater at T4 than T0 (P = 0.038). The beef from SM had 7% greater TBARS than IM and OM (P = 0.003). Livery odor was less intense in raw beef from OM when compared to SM and IM (P ≤ 0.047). Sour odor in raw beef, and livery flavor in cooked beef was increased from T0 to T4 (P ≤ 0.035). Principal component analysis of descriptive sensory attributes indicated that FC and TEAC could predict partial livery flavor in cooked beef, but not off-odors in raw beef.

Formation and Accumulation of Acetaldehyde and Strecker Aldehydes during Red Wine Oxidation.

The main aim of the present work is to study the accumulation of acetaldehyde and Strecker aldehydes (isobutyraldehyde, 2-methylbutanal, isovaleraldehyde, methional, phenylacetaldehyde) during the oxidation of red wines, and to relate the patterns of accumulation to the wine chemical composition. For that, eight different wines, extensively chemically characterized, were subjected at 25°C to three different controlled O2 exposure conditions: low (10 mg L-1) and medium or high (the stoichiometrically required amount to oxidize all wine total SO2 plus 18 or 32 mg L-1, respectively). Levels of volatile aldehydes and carbonyls were then determined and processed by different statistical techniques. Results showed that young wines (<2 years-old bottled wines) hardly accumulate any acetaldehyde regardless of the O2 consumed. In contrast, aged wines (>3 years-old bottled wines) accumulated acetaldehyde while their content in SO2 was not null, and the aged wine containing lowest polyphenols accumulated it throughout the whole process. Models suggest that the ability of a wine to accumulate acetaldehyde is positively related to its content in combined SO2, in epigallocatechin and to the mean degree of polymerization, and negatively to its content in Aldehyde Reactive Polyphenols (ARPs) which, attending to our models, are anthocyanins and small tannins. The accumulation of Strecker aldehydes is directly proportional to the wine content in the amino acid precursor, being the proportionality factor much higher for aged wines, except for phenylacetaldehyde, for which the opposite pattern was observed. Models suggest that non-aromatic Strecker aldehydes share with acetaldehyde a strong affinity toward ARPs and that the specific pattern of phenylacetaldehyde is likely due to a much reduced reactivity toward ARPs, to the possibility that diacetyl induces Strecker degradation of phenyl alanine and to the potential higher reactivity of this amino acid to some quinones derived from catechin. All this makes that this aldehyde accumulates with intensity, particularly in young wines, shortly after wine SO2 is depleted.

Characterization of Odorous and Potentially Harmful Substances in Artists' Acrylic Paint.

Acrylic paints are fast drying water based paints that are easy to handle and have a high covering capacity and therefore possess many characteristics that make them applicable in a wide range of applications, such as varnishes or artists paints. Due to their emitted volatile organic compounds, these paints are associated with different work-related diseases and are known to emit an unpleasant odor. In this study six acrylic paints for artists were analyzed regarding their odor-active constituents. Therefore, the samples were extracted with dichloromethane and purified via solvent assisted flavor evaporation prior to analysis of the distillates by gas chromatography-mass spectrometry (GC-MS), gas chromatography-olfactometry (GC-O), and GC-GC-MS/O. Additionally all samples were sensorially characterized by a trained sensory panel. The identified odorous substances were primarily benzene derivatives (styrene, ethylbenzene, allylbenzene, propylbenzene) with a plastic-like, aromatic and solvent-like odor. Thereby, polycyclic aromatic hydrocarbons (naphthalene, indane, and tetralin derivatives) contributed to the plastic- and mothball-like odor whereas acrylic monomers (butyl acrylate) were found to be responsible for a mushroom-like and geranium leaf-like odor. As most of these substances are also known to be harmful, a reduction or replacement of these substances by less toxic and non-odor active ingredients is likely to turn out to be advisable in order to reduce the odor and potential negative physiological effects of paints.

The effects of copper fining on the wine content in sulfur off-odors and on their evolution during accelerated anoxic storage.

Three different red wines with reductive character have been treated with two different doses of copper sulfate (0.06 and 0.5mg/L) and with a commercial copper-containing product at the recommended dose (0.6mg/L). Wines were in contact with copper one week, centrifuged and stored at 50°C in strict anoxia for 2weeks (up to 7 in one case). Brine-releasable (BR-) and free fractions of Volatile Sulfur Compounds were determined throughout the process. Relevant increases of BR-H2S suggest that those wines contained other H2S precursors non-detectable by the brine dilution method. Copper treatments had two major effects: 1) immediate decrease the levels of free H2S and methanethiol (MeSH); 2) slow the rate at which free H2S (not MeSH) increases during anoxic storage. After 7weeks of anoxia levels of free H2S and MeSH were high and similar regardless of the copper treatment. Higher copper doses could induce the accumulation of BR-H2S.

Formation and Release of H2S, Methanethiol, and Dimethylsulfide during the Anoxic Storage of Wines at Room Temperature.

A total of 21 different wines (13 reds, 5 whites, and 3 rosés) were kept at 25 °C in anoxia for 379 days. Free and total forms of H2S and methanethiol (MeSH) and dimethylsulfide (DMS) were measured initially and after 117, 221, and 379 days of storage. Levels of free H2S, free and total MeSH, and DMS continuously increased during storage, while levels of total H2S remained essentially unchanged. Average increases of free H2S amount to 6.2 µg/L (from 1.1 to 12.9 µg/L), those of free MeSH to 1.6 µg/L (from 0.7 to 3.5 µg/L), and those of total MeSH to 1.9 µg/L (from 1.1 to 3.0 µg/L), whereas those of DMS were 27.8 µg/L (from 11 to 69 µg/L). The fraction of H2S under free forms significantly increased, suggesting that release is a major factor explaining H2S increases. All increases can be satisfactorily predicted from data obtained at 50 °C.

Quantitative analysis of free and bonded forms of volatile sulfur compouds in wine. Basic methodologies and evidences showing the existence of reversible cation-complexed forms.

This paper examines first some basic aspects critical to the analysis of Volatile Sulfur Compounds (VSCs), such as the analytical characteristics of the GC-pFPD system and the stability of the different standard solutions required for a proper calibration. Following, a direct static headspace analytical method for the determination of exclusively free forms of VSCs has been developed. Method repeatability is better than 4%, detection limits for main analytes are below 0.5µgL(-1), and the method dynamic linear range (r(2)>0.99) is expanded by controlling the split ratio in the chromatographic inlet to cover the natural range of occurrence of these compounds in wines. The method gives reliable estimates of headspace concentrations but, as expected, suffers from strong matrix effects with recoveries ranging from 0 to 100% or from 60 to 100 in the cases of H2S and the other mercaptans, respectively. This demonstrates the existence of strong interactions of these compounds with different matrix components. The complexing ability of Cu(2+) and to a lower extent Fe(2+) and Zn(2+) has been experimentally checked. A previously developed method in which the wine is strongly diluted with brine and the volatiles are preconcentrated by HS-SPME, was found to give a reliable estimation of the total amount (free+complexed) of mercaptans, demonstrating that metal-mercaptan complexes are reversible. The comparative analysis of different wines by the two procedures reveals that in normal wines H2S and methanethiol can be complexed at levels above 99%, with averages around 97% for H2S and 75% for methanethiol, while thioethers such as dimethyl sulfide (DMS) are not complexed. Overall, the proposed strategy may be generalized to understand problems caused by VSCs in different matrices.