Effect of methanethiol on process performance, selectivity and diversity of sulfur-oxidizing bacteria in a dual bioreactor gas biodesulfurization system.

This study provides important new insights on how to achieve high sulfur selectivities and stable gas biodesulfurization process operation in the presence of both methanethiol and H2S in the feed gas. On the basis of previous research, we hypothesized that a dual bioreactor lineup (with an added anaerobic bioreactor) would favor sulfur-oxidizing bacteria (SOB) that yield a higher sulfur selectivity. Therefore, the focus of the present study was to enrich thiol-resistant SOB that can withstand methanethiol, the most prevalent and toxic thiol in sulfur-containing industrial off gases. In addition, the effect of process conditions on the SOB population dynamics was investigated. The results confirmed that thiol-resistant SOB became dominant with a concomitant increase of the sulfur selectivity from 75 mol% to 90 mol% at a loading rate of 2 mM S methanethiol day-1. The abundant SOB in the inoculum - Thioalkalivibrio sulfidiphilus - was first outcompeted by Alkalilimnicola ehrlichii after which Thioalkalibacter halophilus eventually became the most abundant species. Furthermore, we found that the actual electron donor in our lab-scale biodesulfurization system was polysulfide, and not the primarily supplied sulfide.

Effect of dimethyl disulfide on the sulfur formation and microbial community composition during the biological H2S removal from sour gas streams.

Removal of organic and inorganic sulfur compounds from sour gases is required because of their toxicity and atmospheric pollution. The most common are hydrogen sulfide (H2S) and methanethiol (MT). Under oxygen-limiting conditions about 92 mol% of sulfide is oxidized to sulfur by haloalkaliphilic sulfur-oxidizing bacteria (SOB), whilst the remainder is oxidized either biologically to sulfate or chemically to thiosulfate. MT is spontaneously oxidized to dimethyl disulfide (DMDS), which was found to inhibit the oxidation of sulfide to sulfate. Hence, we assessed the effect of DMDS on product formation in a lab-scale biodesulfurization setup. DMDS was quantified using a newly, in-house developed analytical method. Subsequently, a chemical reaction mechanism was proposed for the formation of methanethiol and dimethyl trisulfide from the reaction between sulfide and DMDS. Addition of DMDS resulted in significant inhibition of sulfate formation, leading to 96 mol% of sulfur formation. In addition, a reduction in the dominating haloalkaliphilic SOB species, Thioalkalivibrio sulfidiphilus, was observed in favor of Thioalkaibacter halophilus as a more DMDS-tolerant with the 50 % inhibition coefficient at 2.37 mM DMDS.

Development of a Solid-Phase Microextraction-Gas Chromatography/Mass Spectrometry Method for Quantifying Nitrogen-Heterocyclic Volatile Aroma Compounds: Application to Spirit and Wood Matrices.

Over wood aging, matured spirits developed a complex aromatic bouquet where roasted-like notes were often perceived. Since many nitrogen heterocycles were related to these olfactory nuances, a headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography-mass spectrometry was developed and validated to quantify them in both spirit and wood matrices. The various parameters affecting the extraction of the analytes from both spirit and wood samples were first investigated (i.e., fiber coating phase, dilution, pH and volume sample, adding salt, extraction time and temperature, and incubation time) to determine the best compromise for a single-run analysis of the whole set of studied compounds. Good linearity (R2 > 0.99), repeatability, reproducibility, accuracy and low detection, and quantification limits were obtained, making this analytical method a suitable tool for routine analysis of the selected nitrogen compounds. Fifteen pyrazines, three pyrroles, and three quinolines were quantified in a series of oak wood and commercial spirit samples where some of them were identified for the first time. The significant impact of some barrel features and the spirit in-wood maturation step on the N-heterocycle profile in both matrices were finally discussed.

Effect of Vine Water and Nitrogen Status, as Well as Temperature, on Some Aroma Compounds of Aged Red Bordeaux Wines.

Wine aging bouquet is defined as a positive, complex evolution of aromas during bottle aging. The aim of this study was to look for the link between some of the vine status parameters and the development, during wine aging, of volatile compounds such as DMS, tabanones, and some wine aromatic heterocycles. The potential influence of air temperature was investigated as well as vine nitrogen and water status. Wines were obtained by microvinification from plots of Vitis vinifera L. cv. Merlot, Cabernet-Sauvignon, and Cabernet franc, over vintages from 1996 to 2007, and cellar-aged until 2014. Wine aging aromas were quantified using gas chromotography-mass spectrometry. The effects of the vintage and vine water and nitrogen status were greater than the varietal effects. The nine aroma compounds measured showed very high levels in the 2003 vintage. The results revealed a positive link between vine nitrogen status and dimethyl-sulfide and N, S, O-heterocycle levels measured in the aged wines. Levels of 4-[2-butylidene]-3,5,5-trimethyl-2-cyclohexen-1-one and 4-[( 3E)-1-butylidene]-3,5,5-trimethyl-2-cyclohexen-1-one (megastigmatrienones; tabanone) isomers increased when the vines were affected by a water deficit.

Dual solid-phase and stir bar sorptive extraction combined with gas chromatography-mass spectrometry analysis provides a suitable tool for assaying limonene-derived mint aroma compounds in red wine.

A novel analytical method was developed for quantitative determination of eight limonene-derived monoterpenes responsible for the mint aroma in red wine. As these aromatic compounds are present at trace levels, a new dual extraction approach was proposed, combining solid-phase extraction (SPE) and stir bar sorptive extraction (SBSE), followed by gas chromatography-mass spectrometry analysis. The various parameters affecting the efficiency of extracting the analytes from wine samples in both the SPE and SBSE steps were first investigated, to determine the best compromise for the simultaneous analysis of the compounds studied. Following preliminary optimization of the dilution factor, phase ratio, and methanol content in the SBSE sample, cartridge sorbent mass, type of solvent, elution volume, and wine sample volume in the pre-concentration SPE step were studied. Highest response values were obtained when a 90 mL wine sample was extracted on a 500 mg SPE C18 cartridge and eluted with 1.5 mL methanol. The wine extract was then diluted in 10 mL water to obtain a final methanol content of 15% before the SBSE step. Good linearity, repeatability, reproducibility, accuracy and the required low detection and quantification limits were obtained under the conditions described, making this SPE-SBSE combination a suitable, powerful tool for routine analysis of the selected limonene-derived mint aroma compounds in large series of wine samples. Finally, the validated method was applied to 15 commercial red Bordeaux wines, aged from 3 to 23 years. Most of the compounds studied, present within the ng.L-1 range, were easily quantified for the first time in wine.

Vine Water Deficit Impacts Aging Bouquet in Fine Red Bordeaux Wine.

The aim of this study was to investigate the influence of vine water status on bouquet typicality, revealed after aging, and the perception of three aromatic notes (mint, truffle, and undergrowth) in bottled fine red Bordeaux wines. To address the issue of the role of vine water deficit in the overall quality of fine aged wines, a large set of wines from four Bordeaux appellations were subjected to sensory analysis. As vine water status can be characterized by carbon isotope discrimination (δ13C), this ratio was quantified for each wine studied. Statistical analyses combining δ13C and sensory data highlighted that δ13C-values discriminated effectively between the most- and least-typical wines. In addition, Principal Component Analysis (PCA) revealed correlations between δ13C-values and truffle, undergrowth, and mint aromatic notes, three characteristics of the red Bordeaux wine aging bouquet. These correlations were confirmed to be significant using a Spearman statistical test. This study highlighted for the first time that vine water deficit positively relates to the perception of aging bouquet typicality, as well as the expression of its key aromatic nuances.

First identification of three p-menthane lactones and their potential precursor, menthofuran, in red wines.

The p-menthane lactones constitute a family of powerful odorants, including the isomers of mintlactone and menthofurolactone that occur naturally in peppermint oil, known for their potent, mint-like olfactory properties. These lactones are closely related to the monoterpene-limonene secondary biotransformation and menthofuran has been identified as their common precursor in Mentha species. Using targeted GC-olfactometry and GC-MS analyses, together with quantification methods, we were able to demonstrate, for the first time, the presence of the diastereoisomers of these p-menthane lactones, as well as their common precursor, menthofuran, in red wines. In addition, we linked the presence of those lactones to interesting odorant zones, reminiscent of mint, detected in the studied wine. Although these p-menthane lactones may contribute individually to mint and coconut odors, sensory studies suggested for the first time that their combination at the levels found in the red wine studied resulted in a significant accentuation of freshness and mint notes.

Piperitone Profiling in Fine Red Bordeaux Wines: Geographical Influences in the Bordeaux Region and Enantiomeric Distribution.

Piperitone was recently identified in red Bordeaux wines, and this study was designed to further explore its contribution to wine aroma. Firstly, a geographical origin effect was detected within the Bordeaux region (left versus right banks of the Gironde estuary), with significantly higher mint aroma intensities and piperitone levels in wines from the left bank (Medoc appellations). Statistical analysis of chemical and sensory data highlighted a correlation with the proportion of Cabernet Sauvignon in the wine blends. Accordingly, it was suggested that these sensory and chemical differences may be of varietal origin. Secondly, the contribution of piperitone to minty aromas in the aging bouquet was confirmed by combining both sensory and chemical data from a wide range of red Bordeaux wines. Subsequent investigation of the enantiomeric distribution of piperitone found a significantly higher proportion of the (+)-(6S) enantiomeric form in wines displaying a strong aging bouquet.

Identification of Piperitone as an Aroma Compound Contributing to the Positive Mint Nuances Perceived in Aged Red Bordeaux Wines.

Although a sensory definition of the aging bouquet of red Bordeaux wines was recently established, its chemical transcription has only partially been elucidated. A multiple-step approach, combining sensory evaluations of red Bordeaux wines and aromatic reconstitutions of wine extract fractions, was used to identify the molecular markers involved. One wine with a high aging-bouquet score and a mint nuance has received particular attention. Various reconstitution and omission tests highlighted the contribution of two specific fractions to the intensity of the perception of mint aroma. Gas chromatography coupled to olfactometry and mass spectrometry was applied to the targeted fractions to identify molecular marker(s) responsible for the mint nuance in fine red Bordeaux wines. A similar analytical process was applied to selected fractions of essential oils presenting mint odors to characterize them and interpret the mass spectrometry data. This approach resulted in the detection of piperitone, a monoterpene ketone that, to the best of our knowledge, was reported for the first time as a contributor to the positive mint aroma of aged red Bordeaux wines.

Involvement of Dimethyl Sulfide and Several Polyfunctional Thiols in the Aromatic Expression of the Aging Bouquet of Red Bordeaux Wines.

The development of an aromatic bouquet during fine wine aging depends on complex transformations occurring in a reductive atmosphere, favorable to the formation and preservation of sulfur odorants, such as dimethyl sulfide (DMS) and polyfunctional thiols. The aim of this study was to address their role in the occurrence, evolution, and perceived sensory nuances of the aging bouquet of red Bordeaux wines. These compounds were quantified in 24 wines and scored by a professional wine panel for the degree to which they reflected the aging bouquet olfactory concept. Partial least square (PLS) analysis, combining sensory and quantitative chemical data, predicted that DMS, 2-furanmethanethiol, and 3-sulfanylhexanol concentrations correlated with the typicality score, discriminating highly-typical wines from less-typical ones. Several vintages from three vineyards were then subjected to sensory and chemical analysis to determine how aging bouquet typicality and the intensity of five key aromatic notes (undergrowth, truffle, fresh fruit, toasted, and empyreumatic) evolved during bottle storage in relation to these three sulfur odorants. PCA analysis emphasized their combined impact on aging bouquet typicality and their contribution to undergrowth, truffle, and empyreumatic attributes.