Evolution of 3-mercaptohexanol, hydrogen sulfide, and methyl mercaptan during bottle storage of Sauvignon blanc wines. Effect of glutathione, copper, oxygen exposure, and closure-derived oxygen

The effects of wine composition and postbottling oxygen exposure on 3-mercaptohexanol (3-MH), hydrogen sulfide (H2S), and methyl mercaptan (MeSH) were investigated. A Sauvignon blanc wine with initial copper concentration of 0.1 mg/L was treated with copper sulfate and/or glutathione (GSH) prior to bottling to give final concentrations of 0.3 and 20 mg/L, respectively. The wines were bottled with a synthetic closure previously stored in either ambient air or nitrogen to study the effect of the oxygen normally present in the closure. Bottled wines were stored for 6 months in either air or nitrogen to study the effect of oxygen ingress through the closure. Copper addition resulted in a rapid initial decrease in 3-MH. During storage, a further decrease of 3-MH was observed, which was lower with GSH addition and lowered oxygen exposure. H2S accumulated largely during the second 3 months of bottle storage, with the highest concentrations attained in the wines treated with GSH and copper. Lower oxygen from and through the closure promoted H2S accumulation. The concentration of MeSH was virtually not affected by the experimental variables at 6 months, although differences were observed after 3 months of storage. The implications for wine quality are discussed.     

Nondestructive colorimetric method to determine the oxygen diffusion rate through closures used in winemaking

Oxygen is one of the most important factors determining the aging potential of bottled wine, and oxygen diffusion into bottled wine is extremely dependent on the sealing effectiveness of the closure. A nondestructive colorimetric method was developed to measure oxygen diffusion from 1 to 9.8 mg/L during the postbottling period. This method was used to study oxygen diffusion through different closures available on the market. After 365 days of horizontal storage, only the control bottle was impermeable to atmospheric oxygen; all other closures exhibited variable rates of oxygen diffusion, which were much greater in the first month than in the following months. It was shown that the rate of diffusion was clearly influenced by the type of closure material used.     

Ability of possible DMS precursors to release DMS during wine aging and in the conditions of heat-alkaline treatment

The origin of dimethyl sulfide (DMS) produced during wine aging was examined through different assays. The production of DMS during the model aging of a wine and the concomitant decrease of residual potential DMS (PDMS), as DMS released by heat-alkaline treatment in 0.5 M sodium hydroxide at 100 degrees C for 1 h, were demonstrated. Then, dimethyl sulfoxide (DMSO), methionine sulfoxide (MSO), S-methylmethionine (SMM), and dimethylsulfonium propanoic acid (DMSPA), reported previously as possible DMS precursors, were investigated for their ability to be DMS precursors in wine in the conditions of this model aging and of the heat-alkaline treatment. The results showed that DMSO, MSO, and DMSPA could hardly be DMS precursors in the conditions used, whereas SMM appeared to be a good candidate. Finally, the use of [(2)H(6)]-DMSPA as an internal standard for PDMS determination was proposed, because it provided better reproducibility than [(2)H(6)]-DMS used as an external standard.     

Contribution of dimethyl sulfide to the aroma of Syrah and Grenache Noir wines and estimation of its potential in grapes of these varieties

The contribution of dimethyl sulfide (DMS) to the aroma of Syrah and Grenache Noir wines from the Rhone Valley of France was investigated by sensory analysis, and its levels in these wines were measured. The potential DMS in the corresponding grapes and wines, susceptible to release during wine aging, was evaluated. Free DMS and potential DMS assessed by a heat-alkaline treatment were measured in grape juices and wines by SPME-GC-MS using methods previously reported and slightly modified. A relationship between potential DMS from grapes and the total DMS levels in wine was demonstrated. Furthermore, a linear regression between the ratio of free DMS levels to these total DMS levels in wine and time of storage was found. Free and potential DMS levels in grapes and wines depended on grape variety, vintage, and vine location. DMS imparted a noticeable and complex contribution to the aroma of the wines investigated, depending on the mode of sensory perception used, either before or after glass swirling. It significantly enhanced the fruity notes of the wines, and additional truffle and black olive notes.     

Gas chromatographic identification of sulfur gases in soil atmospheres

Simple gas Chromatographic methods for identification of sulfur gases in soil atmospheres are described. They involve the use of a flame photometric detector fitted with a sulfur filter and of Teflon columns packed with Chromosorb T and Deactigel. The methods permit identification of 13 volatile sulfur compounds (sulfur dioxide, hydrogen Sulfide, carbon disulfide, carbonyl sulfide, sulfur hexafluoride, methyl mercaptan, ethyl mercaptan, n-butyl mercaptan, dimethyl sulfide, ethyl methyl sulfide, diethyl sulfide, dimethyl disulfide, and diethyl disulfide) in air containing trace (nanogram) amounts of these compounds, and they are not subject to interference by various gases known to be evolved from soils under aerobic or anaerobic conditions. The Deactigel column is not required if the gas mixture analyzed does not contain hydrogen sulfide or carbonyl sulfide.     

Influence of some technological parameters on the formation of dimethyl sulfide, 2-mercaptoethanol,methionol, and dimethyl sulfone in port wines

Volatile sulfur compounds of 15 young port wines and 12 old port wines were determined. As there is a great difference in the pool of sulfur compounds between the two groups of wines, an experimental protocol was performed to determine which technological parameter (dissolved O(2), free SO(2) levels, pH, and time/temperature) was related with the formation/consumption of these compounds. Four sulfur compounds were selected for this purpose: dimethyl sulfide, 2-mercaptoethanol, dimethyl sulfone, and methionol. The synergistic effects of increasing temperature and O(2) at lower pH had the largest impact. Dimethyl sulfide was formed during the experimental period in the presence of O(2). Dimethyl sulfone had the same behavior. Methionol decreased significantly in the presence of O(2), but no methional was formed. 2-Mercaptoethanol, considered to be an important "off-flavor" in dry wines, also decreased during the experimental period (54 days) in the presence of O(2), and the respective disulfide was formed. These results corroborate the fact that old port wine (barrel aged) never develops "off-flavors" associated with the presence of methionol (cauliflower), 2-mercaptoethanol (rubber/burnt), or methional (cooked potato). In fact, temperature and oxygen are the major factors in the consumption of these molecules. However, some notes of "quince" and "metallic" can appear during port wine aging, and these can be associated with the presence of dimethyl sulfide.     

Evolution of volatile sulfur compounds from soils treated with sulfur-containing organic materials

Release of volatile S compounds from soils treated with S-containing organic materials was studied by sensitive gas chromatographic techniques. Methyl mercaptan, dimethyl sulfide, dimethyl disulfide, carbonyl sulfide and carbon disulfide were identified as gaseous products of decomposition of animal manures, sewage sludges and plant materials in soils under aerobic or waterlogged conditions. No release of hydrogen sulfide was detected. Most of the S volatilized from soils treated with sludges was in the form of dimethyl sulfide and dimethyl disulfide. whereas most of the S volatilized from soils treated with manures and plant materials was in the form of methyl mercaptan and dimethyl sulfide. More S compounds were released, and more S was volatilized, by decomposition of manures, sludges or plant materials in soils under waterlogged conditions than by decomposition under aerobic conditions. When calculated as a percentage of the S added as organic material, the average amount of S volatilized under aerobic or waterlogged conditions was < 0.2% < 0.5% and < 3.4% for the sludges, manures and plant materials, respectively. The five volatile S compounds produced by decomposition of manures, sludges and plant materials in soils under aerobic and waterlogged conditions also were produced by decomposition of plant proteins (zein, gluten and gliadin). It is concluded that the volatile S compounds released by decomposition of the above organic materials in soils are largely, if not entirely, produced by microbial degradation of methionine and cystine in these materials.     

预处理加工对西兰花茎叶汁挥发性成分的影响

为研究热烫、冻融、超声3种预处理方式对西兰花茎叶汁挥发性成分的影响,本试验利用顶空固相微萃取-气相质谱联用仪对不同预处理加工后的西兰花茎叶制成的西兰花茎叶汁中挥发性成分进行测定。结果表明,西兰花茎叶汁的主要异味成分为己醛、庚醛、壬醛、(E)-2-己烯醛、(E,E)-2,4-庚二烯醛、1-戊醇、1-辛醇、1-己醇、(E)-3-己烯-1-醇、甲硫醇、2-乙基噻吩、硫氰酸甲酯、二甲基二硫醚、β-紫罗酮、6-甲基-5-庚烯-2-酮。与超声预处理相比,热烫和冻融处理可以较好地降低西兰花茎叶汁中挥发性成分的种类和含量。与未进行预处理的对照组相比,热烫处理的西兰花茎叶汁中虽然检出了甲硫醇和二甲基二硫醚,但醛类含量减少,酯类含量增加,此外,与冻融处理相比,热烫硫化物含量更低。本研究为西兰花茎叶的果蔬汁开发提供了理论依据。     

Identification of characteristic aroma components of Thai fried chili paste

Three forms of Thai fried chili pastes (CP) were prepared, consisting of an unheated CP (UH-CP), a CP heated at 100 degrees C for 25 min (H25-CP, typical product), and a CP excessively heated for 50 min (H50-CP). The potent odorants in the CPs were investigated by two gas chromatography-olfactometry methods: dynamic headspace dilution analysis (DHDA) and aroma extract dilution analysis (AEDA). DHDA revealed that the predominant odorants in heated CPs were mainly sulfur-containing compounds, followed by lipid-derived compounds, Strecker aldehydes, and Maillard reaction products. Dimethyl sulfide, allyl mercaptan, 2- (or 3-) methylbutanal, ally methyl sulfide, 2,3-butanedione, 3,3'-thiobis(1-propene), and methyl propyl disulfide were among the most potent headspace odorants detected by DHDA. By AEDA, 2-vinyl-4 H-1,3-dithiin and diallyl trisulfide had the highest FD factors in H25-CP. On the basis of their high FD factors by both GCO methods, the predominant odorants in H25-CP were 3-vinyl-4 H-1,2-dithiin, allyl methyl disulfide, and allyl methyl trisulfide. Furthermore, dimethyl trisulfide and diallyl disulfide had the highest odor activity values in H25-CP, suggesting that these were also potent odorants in CP. In addition, methional, 3-methylbutanoic acid, 4-hydroxy-2,5-dimethyl-3-(2 H)-furanone, and 3-hydroxy-4,5-dimethyl-2( 5H)-furanone (sotolon) were indicated as potent thermally derived odorants of H25-CP.     

Synthesis and stable isotope dilution assay of ethanethiol and diethyl disulfide in wine using solid phase microextraction. Effect of aging on their levels in wine

Ethanethiol and diethyl disulfide (DEDS) most often occurred at levels above their olfactive threshold in wines with nauseous sulfur-linked smells. As ethanethiol is very oxidizable and chemically reactive, a stable isotopic dilution analysis of both ethanethiol and its disulfide in wines using solid phase microextraction and GC-MS was developed. The latter involved the determination of the proportion of DEDS formed by oxidation of the thiol during the analysis conditions, which was obtained by the use of two differently labeled disulfide standards. An original synthesis of labeled ethanethiol standards in conditions minimizing oxidation was developed, and the corresponding labeled diethyl disulfides were obtained from these thiols. This analytical method was used to follow the levels of these sulfur compounds during aging in a young red wine spiked with ethanethiol and added with enological tannins, with or without oxygen addition. The total levels of these two sulfur compounds were shown to decrease steadily after 60 days of aging, up to 83%. The effect of oxygen sped this decrease, but the effect of enological tannins was very slight. Residual ethanethiol was detected in its disulfide form from approximately 36% in the nonoxygenated wines to 69% in the oxygenated samples.     

Formation of volatile sulfur compounds by microbial decomposition of sulfur-containing amino acids in soils

Evolution of volatile sulfur compounds from soils treated with S-containing amino acids was studied by sensitive gas chromatographic techniques involving use of a flame photometric detector fitted with a sulfur filter. The following volatile sulfur compounds were identified as products of microbial decomposition of S-containing amino acids in soils under aerobic or waterlogged conditions: methyl mercaptan, dimethyl sulfide and dimethyl disulfide (evolved from soils treated with methionine, methionine sulfoxide, methionine sulfone or S-methyl cysteine); ethyl mercaptan, ethyl methyl sulfide and diethyl disulfide (evolved from soils treated with ethionine or S-ethyl cysteine); and carbon disulfide (evolved from soils treated with cystine, cysteine, lanthionine or djenkolic acid). Small amounts of dimethyl sulfide and carbon disulfide were evolved from soils treated with homocystine, and trace amounts of carbonyl sulfide were evolved from soils treated with lanthionine or djenkolic acid. No volatile sulfur compounds were evolved from soils treated with cysteic acid, taurine, or S-methyl methionine. The amounts of sulfur volatilized from soils treated with the 14 S-containing amino acids studied represented from less than 0·1 per cent to more than 50 per cent of the sulfur added as amino acid. Hydrogen sulfide could not be detected as a gaseous product of microbial decomposition of S-containing amino acids in soils under aerobic or waterlogged conditions.     

Changes in the sotolon content of dry white wines during barrel and bottle aging

GC-MS in electron ionization mode (EI) was used as a simple, sensitive method for assaying sotolon [4,5-dimethyl-3-hydroxy-2(5) H-furanone] in various dry white wines. The impact of barrel-aging conditions, that is, whether yeast lees were present or not, on the formation of sotolon in dry white wines was then studied. The sotolon content was highest in dry white wines aged in new barrels without lees, often exceeding the perception threshold (8 microg/L). These results demonstrated that yeast lees were capable of minimizing the formation of sotolon in dry white wines during aging. The sotolon and oxygen contents of several bottle of the same white wine were also compared 7 years after bottling. At the range of dissolved oxygen concentrations generally measured, between 5 and 100 microg/L, the sotolon content remained below its perception threshold in wine. The perception threshold was exceeded only in wines with oxygen concentrations above 500 microg/L. The presence of dissolved oxygen in the wine samples analyzed also resulted in a decrease in their free sulfur dioxide content.     

Impact of storage position on oxygen ingress through different closures into wine bottles

Wine bottle aging is extremely dependent on the oxygen barrier properties of closures. Kinetics of oxygen ingress through different closures into bottles was measured by a nondestructive colorimetric method from 0.25 to 2.5 mL of oxygen. After 12, 24, and 36 months of storage, only the control (glass bottle ampule) was airtight. Other closures displayed different oxygen ingress rates, which were clearly influenced by the closure type and were independent of bottle storage position (upright, laid down) for most of the closures tested, at least during the first 24 months of the experiment under controlled conditions. The oxygen ingress rates into bottles were lowest in screw caps and "technical" corks, intermediate in conventional natural cork stoppers, and highest in the synthetic closures.     

Inhibition of nitrification in soils by volatile sulfur compounds

Carbon disulfide, dimethyl disulfide, methyl mercaptan, dimethyl sulfide, and hydrogen sulfide retard nitrification of ammonium in soils incubated in closed systems. The inhibitory effects of these volatile sulfur compounds on nitrification decrease in the order listed. Hydrogen sulfide is a relatively weak inhibitor of nitrification, but carbon disulfide is considerably more effective than patented nitrification inhibitors (N-Serve. AM, and ST) for inhibition of nitrification in closed systems.It is concluded from the work reported that the inhibitory effects of methionine, cystine, cysteine, and other nonvolatile organic sulfur compounds on nitrification in soils may be at least partly due to decomposition of these compounds by soil microorganisms with formation of volatile sulfur compounds that retard nitrification.     

Formation of methyl mercaptan in paddy soils I

It is well known that methyl mercaptan is porduced by the microbiological decomposition of methionine1),2),3). According to Kondo ⁴⁾ and Onitake ¹⁾not only hydrogen sulfide, but also methyl mercaptan were produced from cystine by E. coli and Proteus vulgaris in the medium containing one of glucose, lactose, sucrose, glycerin or histidine. Moreover, Onitake ¹⁾ found that methyl mercaptan was produced by the action of E. coli in the medium containing hydrogen sulfide and a trace of ethyl alcohol, and that evolution of methyl mercaptan began only 5 minutes after the start of experiment in the medium containing methionine, but it began after 12hrs in the medium containing 1-cystine and glucose. According to Birkinshaw, Findlay and Webb⁵⁾ methyl mercaptan was found in the medium containing glucose, sulfate and other mineral salts, inoculated by Schizophyllum commune. In the same cultural condition as given above, methyl mercaptan, dimethyl sulfide, and dimethyl disulfide were detected by Challenger and Chartons ⁵⁾ from the data presented above, in addition to microbiological formation of methyl mercaptan from methionine, the possibility cannot be excluded of methyl mercaptan formation by microbes from cystine, sulfate or hydrogen sulfide in the medium containing one of organic compounds such as sugars, glycerin, histidine and ethyl alcohol, etc.     

Peat Biofilters in Long-Term Experiments for Removing Odorous Sulphur Compounds

Peat was employed as a biological filter material for the removal of hydrogen sulphide (H_2> S) dimethyl sulphide (Me₂S) and methyl mercaptan (MeSH) from odorous ventilation air. Removal of H₂S was possible without the need to inoculate the filter material with oxidizing microbes whereas Me₂S required inoculation for degradation. The removal of Me₂S was decreased as a result of MeSH addition. Liming of the filter material, i.e., addition of calcium hydroxide, increased removal efficiency and activated the oxidation of H₂S without any adaptation period. As a consequence of the poor Me₂S removal efficiency of natural peat, a limed and inoculated biofilter was needed to purify mixtures of gases containing sulphur. The highest H₂S load tested with limed but otherwise natural peat was 136 g-S m^-3 day^-1, yielding a 99 % reduction. The maximum Me₂S elimination capacity with limed and inoculated peat was 175 g-S m^-3day^-1, but removal became unstable when the load exceeded 150 g-S m^-3day^-1. The maximum MeSH load tested was 107 g-S m^-3day^-1, yielding 98 % removal.     

Aging effects and grape variety dependence on the content of sulfur volatiles in wine

Thirteen sulfur compounds (boiling points from 35 to 231 degrees C), usually considered as possible off-flavoring volatiles, were quantified by a concurrent headspace-solid phase microextraction method coupled with gas chromatography-mass spectrometry (HS-SPME/GC-MS) on 80 not off-flavoring wines of four varieties (Merlot, Marzemino, and Teroldego as red wines and Chardonnay as a white one) and of five vintages produced in the North Italian Trentino region. The results of the research, the first Italian data-bank per variety on such volatiles, allow us to make a comparison with the data of other winegrowing areas, to investigate the aging effect on the considered volatiles, and, finally, to try a variety discrimination using statistical procedures. Dimethyl sulfide, 3-(methylthio)-1-propanol, diethyl sulfide, and diethyl disulfide were found to increase with time whereas 2-mercaptoethanol and ethylmercaptan showed a decreasing trend. Furthermore, the concentration of several compounds was found to be dependent on the variety. For instance, sulfide, disulfides, benzothiazole, and thioalcohols are at higher levels in Merlot wines, whereas thiols and thioacetates are more abundant in Marzemino and Teroldego wines. Chardonnay products, well apart from the other wines, are the poorest in 3-(methylthio)-1-propanol and rather rich in dimethyl disulfide and in diethyl disulfide, mostly in the aged wines. Applying the principal component analysis to the data, it was possible to demonstrate that Chardonnay and Merlot wines are well-discriminated from the Italian native varietal wines, which on their turn are only partially distinguishable among them. A contribution of these compounds to the variety characteristics of wine is reasonable.     

Pilot-scale test of a soil filter for treatment of malodorous gas

Abstract. A pilot-scale test confirmed that malodorous air containing 600 mg l⁻¹ ammonia can be passed through a soil filter with 98.5% removal efficiency. Furthermore, the concentrations of methyl mercaptan, dimethyl sulfide, dimethyl disulfide, actaldehyde, and trimethyl amine were also significantly reduced using soil as a filter. The tests provide technical information for planning of industrial-scale soil filters: linear velocity, bed depth, properties of soil, reliability, and effects of soil deodorization on various types of odorous substances. It is concluded that the soil can be an effective filter to remove noxious and malodorous gases derived from industrial processes.     

风干预处理对堆肥腐熟度及臭气排放量的影响

该研究以风干猪粪堆肥为处理,以新鲜猪粪堆肥为对照,在秸秆调理相同C/N基础上,对两个处理腐熟度和臭气排放进行比较分析。从温度、p H值、电导率和发芽率来看,利用新鲜猪粪和风干猪粪堆肥所得的产品均能达到腐熟和无害化标准;在硫化氢、羰基硫、二硫化碳、甲硫醚、乙硫醚、二甲二硫、甲硫醇和乙硫醇几种含硫臭气中,甲硫醚和二甲二硫占96%以上;风干猪粪堆肥比新鲜猪粪堆肥少排放71.09%的氨气,66.11%的甲硫醚和9.66%的二甲二硫。在不考虑风干环节存在的问题条件下,与新鲜猪粪堆肥相比,风干猪粪堆肥堆肥时间短,在堆肥品质提高的基础上,堆肥产品产量增加60%。通过降低水分和体积风干猪粪运输成本降低1/3,且对环境影响小,是远距离资源化处理畜禽粪便的较好途径。     

Mercaptan-capturing properties of mushrooms.

Mercaptan-capturing properties of 33 kinds of mushrooms were measured. The mushrooms having a high capturing ability toward methyl mercaptan (MeSH) were Agaricus bisporus, A. campestris, Boletus fraternus, B. subvelutipes, Gyrodon lividus, Leccinum scabrum, Suillus grevillei, Morchella esculenta, Russula nigricans, Hypholoma sublateritium, and Lyophyllum sykosporum. These are liable to change their color when injured. The mixture of their acetone powders, which contain polyphenol oxidases, and phenolic compounds such as tyrosine, gamma-L-glutaminyl-4-hydroxybenzene (GHB), DOPA, variegatic acid, grevillin B and C, and pigments, and fluorescent compounds from H. sublateritium also showed high MeSH-capturing properties. 2,5-Bis(methylthio)-DOPA was isolated from the reaction mixture of tyrosine and MeSH with tyrosinase, and the existence of 2- and 5-methylthio-DOPAs was also suggested. Furthermore, acetone powders from fruits and vegetables oxidized the above diphenolic compounds to bind MeSH.