Amelioration of smoke taint in wine by reverse osmosis and solid phase adsorption

Background and Aims: Wines made from grapes harvested from vineyards exposed to bushfire smoke can exhibit objectionable ‘smoky’, ‘cold ash’, ‘medicinal’ and ‘ashy’ aroma and flavour characters. This study evaluated a combined reverse osmosis and solid phase adsorption process as a potential amelioration method for the treatment of smoke‐tainted wines. Methods and Results: Smoke‐tainted wines were treated using either pilot or commercial scale reverse osmosis systems and the chemical composition and sensory properties of wine compared before and after treatment. The concentrations of smoke‐derived volatile phenols, including marker compounds, guaiacol and 4‐methylguaiacol, decreased significantly with treatment. As a consequence, diminished smoke‐related sensory attributes enabled treated wines to be readily differentiated from untreated wines. However, the taint was found to slowly return with time, likely because of hydrolysis of glycoconjugate precursors, which were not removed during the treatment process. Conclusions: Reverse osmosis and solid phase adsorption reduced the concentration of smoked‐derived volatile phenols and improved the sensory attributes of smoke‐tainted wines. Significance of the Study: This is the first study to evaluate the amelioration of smoke taint in wine using reverse osmosis and solid phase adsorption.     

Amelioration of smoke taint in wine by treatment with commercial fining agents

Background and Aims: Fermentation of smoke‐affected grapes can lead to wines that exhibit objectionable smoke‐related sensory attributes, i.e. smoke taint. Fining agents are routinely used at different stages of the winemaking process to address constituents that are considered to adversely affect juice or wine quality. This study aimed to evaluate the efficacy of commercial fining agents in reducing the concentration of volatile phenols and the intensity of sensory attributes associated with smoke‐tainted wine. Methods and Results: Smoke‐affected wines were treated with a range of fining agents, two of which, an activated carbon and a synthetic mineral, were found to appreciably ameliorate the taint. Treated wines contained a significantly lower level of smoke‐derived volatile phenols and exhibited less intense ‘smoke’ and ‘cold ash’ aromas, ‘smoky’ flavour and ‘ashy’ aftertaste, compared with that of untreated (control) wines; with little or no impact on wine colour. Conclusions: Selected fining agents can ameliorate smoke taint in wine. Whereas most fining agents showed poor specificity towards the wine components responsible for smoke taint, some, an activated carbon in particular, were highly effective. Significance of the Study: This research identifies a treatment that can be used to mitigate the impact of grapevine exposure to smoke on wine composition and sensory properties.     

Impact of lignin composition on cell‐wall degradability in an Arabidopsis mutant

An Arabidopsis mutant that does not deposit syringyl‐type lignin was used to test the hypothesis that lignin composition impacts cell‐wall degradability. Two lines of the ferulate‐5‐hydroxylase‐deficient fah1 mutant and the wild‐type control line were grown in the greenhouse. In Experiment 1, the plants were harvested at the mature seed stage. For Experiment 2, plants were harvested 5, 6, 7 and 8 weeks after sowing. In both experiments stems were collected and analysed for cell‐wall concentration and composition, and in vitro degradability of cell‐wall polysaccharide components by rumen micro‐organisms. The absence of syringyl‐type lignin was confirmed for the mutant lines by nitrobenzene oxidation and pyrolysis‐GC‐MS. Lignin concentration was the same for all three Arabidopsis lines, at all stages of maturity. The Arabidopsis stems were similar to forage legumes in that the potentially degradable cell‐wall fraction was very quickly degraded. Cell‐wall polysaccharide degradability did not differ among the Arabidopsis lines in the first experiment after 24‐h fermentations, but the cell‐wall polysaccharides of the fah1‐2 mutant line were less degradable after 96‐h than either the wild‐type or the fah1‐5 mutant. In contrast, in Experiment 2 no differences among lines were found for cell‐wall polysaccharide degradability after either 24‐ or 96‐h fermentations; however, signficantly higher levels of ester‐bound ferulic acid were found in the walls of the fah1 mutant lines. As expected, increasing stem maturity was correlated with reduced degradation of cell‐wall polysaccharides. These experiments indicate that either lignin composition, as measured by syringyl‐to‐guaiacyl ratio, does not alter cell‐wall degradability in Arabidopsis, or that the fah1 mutation has other effects on the cell walls of these mutants such that the impact of the change in syringyl‐to‐guaiacyl ratio is masked. © 1999 Society of Chemical Industry     

Comparison of methods for the analysis of smoke related phenols and their conjugates in grapes and wine

Background and Aims: Australian grape growers and winemakers have typically relied on guaiacol and 4‐methylguaiacol measurements to determine smoke exposure of grapes following bushfires or prescribed burns. However, the guaiacol and 4‐methylguaiacol content of grapes does not always correlate with the extent of taint in resultant wines. This study compared several methods for the analysis of smoke related phenols and their conjugates in grapes and wine, to determine their capacity as diagnostic assays for smoke exposure. Methods and Results: Smoke‐affected grapes were sourced from commercial vineyards exposed to bushfire smoke and from experimental field trials involving the application of smoke to grapevines, and small‐scale wines were made from a number of these samples. Several analytical methods were applied to grapes and wine to determine the concentration of smoke related phenols and their conjugates. Strong correlations were observed between the glycoconjugate content of smoke‐affected grapes and the concentration of guaiacol and 4‐methylguaiacol released following acid hydrolysis of juice. Conclusions: Where smoke‐affected grapes contain low or non‐detectable levels of guaiacol and 4‐methylguaiacol, analytical methods that quantify their glycoconjugate forms (either directly or indirectly) provide a better indication of the extent of smoke exposure. Significance of the Study: This is the first study to compare different methods for assessing smoke exposure in grapes and wine, through analysis of free and bound guaiacol and 4‐methylguaiacol. These methods will allow grape growers and winemakers to more reliably assess smoke exposure of grapes, enabling better informed decisions to be made with regards to harvesting and processing smoke‐affected grapes.     

传统熏烤木材中木质素结构表征及其热解特性

为探究传统熏烤肉制品熏烤时所采用不同化学组成及结构的木材类型对产生有害物质多环芳烃的种类和生成量的影响,以传统熏烤肉制品生产时常用的松木、杨木、榉木、枣木、苹果木5种木材为研究对象,通过红外光谱、拉曼光谱、热重及热重-红外联用分析,考察5种木材中木质素的结构特征及其热解特性。结果表明：5种木材中木质素含量,以及木质素中愈创木基结构单元（G）、紫丁香基结构单元（S）含量均存在差异;热解过程基本可分为3个阶段,主要发生在200～500℃范围内,但是5种木质素的质量损失速率、质量损失温度、热解速率、热解温度均不同,说明不同木质素的热稳定性存在显著差异。熏烤木材中木质素含量,S/G结构含量及侧链结构上差异可导致其热稳定性的不同,而热解特性的不同则进一步影响多环芳烃等有害物的生成。     

Analysis of lignin from oak casks used for the maturation of Scotch whisky

Wood from four types of casks used for the maturation of Scotch whisky was analysed for free vanillin, syringaldehyde, vanillic and syringic acids and for milled wood lignin. Degradation of wood lignin by acidolysis was used to estimate the proportion of intact β-aryl ether linkages present. The yield of milled wood lignin was unaffected by repeated cask use. A comparison of acidolysis yields and the analysis of spirit matured for 3 years in each of the four types of cask indicated that the majority of β-aryl ether linkages in oak lignin are resistant to spirit hydrolysis and that cask exhaustion was not accompanied by significant delignification. Significant reductions in the concentrations of free guaiacyl and syringyl compounds were recorded for used casks and proved the best indicator of cask exhaustion.     

Effect of timing and duration of grapevine exposure to smoke on the composition and sensory properties of wine

Background and Aims:  Grapevine smoke exposure has been reported to produce smoke aromas in wine, resulting in 'smoke taint'. This study describes the application of smoke to field-grown grapevines between veraison and harvest to investigate the effect of timing and duration of smoke exposure on wine composition and sensory attributes.
Methods and Results:  Smoke was applied to grapevines as either a single smoke exposure to different vines at veraison or at 3, 7, 10, 15, 18 or 21 days post-veraison or repeated smoke exposures to the same vines at veraison and then at 3, 7, 10, 15, 18 and 21 days post-veraison. Gas chromatography-mass spectrometry analysis of guaiacol, 4-methylguaiacol, 4-ethylguaiacol and 4-ethylphenol showed elevated levels in all wines produced from fruit from smoked grapevines. Repeated smoke exposures had a cumulative effect on the concentration of these compounds. A trained sensory panel identified the aromas of 'burnt rubber', 'smoked meat', 'leather' and 'disinfectant' in all wines derived from smoke-exposed grapevines but not in control wines.
Conclusions:  Smoke application to field-grown grapevines between veraison and harvest can influence the accumulation of volatile phenols and intensity of smoke aromas in resultant wines. A peak period of vine sensitivity to smoke at 7 days post-veraison is identified. Repeated smoke exposures have a cumulative effect.
Significance of the Study:  This is the first study to report the deliberate and controlled smoke application to field-grown grapevines demonstrating the timing and duration of smoke exposure to significantly affect wine chemical and sensory characters.     

Guaiacol and 4‐methylguaiacol accumulate in wines made from smoke‐affected fruit because of hydrolysis of their conjugates

Background and Aims: Taint in smoke‐exposed grapes have been associated with elevated levels of guaiacol and 4‐methylguaiacol. Previous research has reported guaiacol and 4‐methylguaiacol in both fruits and wines. In some cases, these compounds were not detected, or were detected at low levels in the fruit while high levels were subsequently identified during or after winemaking. Later research indicated that this was due to the presence of glycosidic conjugates. Here we report a method for the routine analysis of guaiacol and 4‐methylguaiacol released after acid hydrolysis of glycoside precursors. Methods and Results: Chardonnay, Merlot, Shiraz, Sangiovese and Cabernet Sauvignon fruits were collected following bushfire events in 2006–2007 in the King Valley wine region of NE Victoria, Australia. Gas chromatography‐mass spectrometry (GC‐MS) was used to detect free guaiacol and 4‐methylguaiacol in both fruits and wines. Low levels of free and bound forms were present in fruit not exposed to smoke. Substantial levels of free guaiacol and 4‐methylguaiacol were detected in the wines made from the smoke‐affected fruits. These compounds increased during bottle storage. Acid hydrolysis of wines and berries resulted in a several‐fold increase in free guaiacol and 4‐methylguaiacol. Conclusions: The validated GC‐MS method is suitable for monitoring free and glycosidically bound guaiacol and 4‐methylguaiacol after acid hydrolysis in both fruits and wines. Acid hydrolysis of wines provided evidence that bound volatiles, most probably glycosidically, act as reserve for guaiacol and 4‐methylguaiacol, which are released during ageing of wines. Significance of the Study: This is the first study published in a refereed journal to demonstrate that smoke taint‐associated volatiles increase during ageing of wine and bound forms of guaiacol and 4‐methylguaiacol represent an aroma reserve for smoke taint in ageing/bottled wines.     

Effect of smoke application to field‐grown Merlot grapevines at key phenological growth stages on wine sensory and chemical properties

Background and Aims: Smoke exposure of grapevines and development of smoke taint in wine are issues of increasing incidence and severity. There is limited understanding of the effect of phenological stage at the time of smoke exposure on taint development. The aim of this study was to demonstrate the variation in smoke uptake and taint development between and within seasons. Methods and Results: Smoke was applied to field‐grown Merlot grapevines at 12 stages of vine development over three growing seasons. Key periods of vine sensitivity to smoke taint in wine were (i) from shoots at 10 cm to full bloom (low levels of smoke taint); (ii) from berries at pea size to the onset of veraison (variable levels of smoke taint); and (iii) between 7 days post‐veraison and harvest (high levels of smoke taint). Conclusions: The severity of taint in wine varied depending on the phenological timing of grapevine smoke exposure. Taint was elevated when exposure occurred between 7 days post‐veraison and harvest. The carry‐over of smoke constituents the following season was not detectable in wine but yields were reduced. Significance of the Study: This is the first study to demonstrate the timing of smoke exposure to critically affect wine chemical and sensory characters. These effects were consistent and reproducible over three seasons.     

Monitoring Phenolic Composition of Maturing Maize Stover by High Performance Liquid Chromatography and Pyrolysis/Gas Chromatography/Mass Spectrometry*

Maize stovers collected every 14 days over an 84-day growth period were subjected to high-performance liquid chromatography with electrochemical detector (HPLC-ED) and pyrolysis/gas chromatography/mass spectrometry (PY/GC/MS) in order to monitor changes in the phenolic composition. Prior to HPLC-ED analyses, ground samples were sequentially extracted with (i) methanol, (ii) 0·1M sodium hydroxide and (iii) 2M sodium hydroxide in the presence of nitrobenzene to separate, respectively, free phenolic monomers, alkali-labile phenolic monomers and alkali-resistant lignin. In turn, solution (ii) was treated with alkaline nitrobenzene to obtain (iv) alkali-labile lignin. Pyrolysis was carried out on ground native samples by using a platinum heated filament pyrolyser. Increases in the absolute phenolic concentrations in the residues of 0·1M sodium hydroxide extraction and in the ratio of alkali-resistant lignin vs total lignin were observed by HPLC-ED during the first 28–42 days of maturation, reaching a steady level in the remaining maturation period. A linear increase of syringyl units vs guaiacyl units was for found the alkali-resistant lignin fraction over the entire period of maturation. Similar trends were showed by PY/GC/MS with regard to relative lignin content and syringyl/guaiacyl ratio. Both techniques showed their usefulness to gauge changes in the phenolic composition during the lignification process.     

烟草木质素结构的二维核磁共振波谱表征

[背景和目的]烟草木质素对烟草品质和安全性有重要影响,为了提高烟草制品的质量,需要探究烟草木质素的化学结构及含量.[方法]利用二维异核单量子相干核磁共振技术(2D HSQC NMR)建立表征烟草木质素的方法,实现烟草木质素的结构表征及半定量分析.[结果](1)烟草样品木质素中共发现10种主要的木质素基本单元及单元间连接...     

Quantitative analysis of glycoconjugate precursors of guaiacol in smoke-affected grapes using liquid chromatography–tandem mass spectrometry based stable isotope dilution analysis

Guaiacol has been shown to accumulate in glycoconjugate forms in the fruit and leaves of grapevines following vineyard exposure to bushfire smoke. To investigate the glycosylation of guaiacol in smoke-affected grapes, a quantitative stable isotope dilution analysis method using liquid chromatography-tandem mass spectrometry was developed and validated, using the [²H₄]-labelled analogue of guaiacol β-d-glucopyranoside as internal standard. The method was subsequently applied to the analysis of grapes sampled from grapevines exposed to either bushfire or experimental smoke, enabling compositional comparisons of guaiacol glycoconjugates in smoke-affected grapes from different varieties to be determined, for the first time.     

GC/MS analysis of lignin monomers,dimers and trimers in liquid smoke flavourings

The common components found in smoke flavourings are carbonyl derivatives, acids, esters and lignin monomers such as alkyl-aryl ethers and phenol derivatives. Recently the presence of lignin dimers has been noted. In addition to these compounds, lignin trimers and new lignin dimers have been detected in the brown layer left by a smoke flavouring on the wall of the receptacle in which it was contained; these compounds tend to migrate towards the wall of the container and have not been previously described as smoke or smoke flavouring components. Lignin trimers and dimers are important in the preservation of smoked foods for their known high antioxidant activity, even higher than that of the lignin monomers. The mass spectral data of a large number of lignin trimers and dimers are given and can be useful for future studies of smoke flavourings and smoked food as well as in beverage studies and for the characterisation of woods to be used in the beverage industry. © 1999 Society of Chemical Industry     

Digestibility of silages in relation to their hydroxycinnamic acid content and lignin composition

BACKGROUND: The effectiveness of the analysis of cell wall‐bound hydroxycinnamic acids and the composition of lignin to evaluate the in vivo digestibility of a silage collection with unknown botanical composition was evaluated. RESULTS: Syringyl units content and total etherified phenols showed the highest correlation coefficients with in vivo dry matter digestibility (IVDMD) (r = ? 0.792 and r = ? 0.703, respectively), while guaiacyl units and total phenols showed the highest correlation coefficients with in vivo organic matter digestibility (IVOMD) (r = ? 0.871 and r = ? 0.817, respectively). Using the above‐mentioned chemical parameters, 10 equations were also developed to predict in vivo digestibility. The prediction of IVDMD produced a high adjusted R² value (0.710) using syringyl, total lignin, etherified total phenols, esterified ferulic acid and total phenol content as predictors. The prediction of IVOMD produced a higher adjusted R² value (0.821) using guaiacyl, total phenols, total ferulic acid and etherified p‐coumaric acid content as predictors. CONCLUSION: Cell wall digestibility depends on a multiplicity of factors and it is not possible to attribute a causal effect on in vivo digestibility to any single factor. However, syringyl and guaiacyl content and etherified phenols emerge as good predictors of digestibility. Copyright © 2010 Society of Chemical Industry     

Characterization of asparagus lignin by HPLC

Lignin is the cell wall component most frequently associated with hardening. Its characterization and quantification are very important to understand the biochemical modifications related to the changes in texture of vegetables such as asparagus (Asparagus officinalis), in which this organoleptic attribute is a very important quality factor. In this study, asparagus lignin from the basal sections of fresh and stored spears was analyzed using 2 methods, the traditional (Klason lignin) and the recently developed derivatization, followed by reductive cleavage (DFRC) method. The latter is a simple and reproducible technique for lignin characterization based on a degradation procedure that produces analyzable monomers and dimers by cleaving alpha- and beta-aryl ethers in lignins. The primary monomers derived from DFRC degradation of lignins are essentially p-coumaryl peracetate, coniferyl peracetate, and sinapyl peracetate. To evaluate the efficiency of the DFRC method, our investigations have been carried on distinct sample types, including wood (data not shown), straw, and asparagus samples. The results have confirmed that lignin composition is affected by plant nature. It has been found that whereas wood samples mostly contain coniferyl units, plant foods, such as straw and asparagus, contain both coniferyl and guaiacyl units.     

有机溶剂法麦草木质素的化学特性研究

用不同浓度的乙酸-水、甲酸-乙酸-水、甲醇-水及乙醇-水溶液处理脱蜡的麦草,获得的木质素采用FT-IR、~1H-NMR、~(13)C-NMR及化学法研究其化学特性,结果表明,有机酸溶液比有机醇溶液脱木素作用更加广泛,能选择性降解麦草中的纤维素、木质素及半纤维素。甲酸对木质素的溶解有显著影响。随着乙酸或甲酸浓度的增加,愈创木基结构单元增加,木质素缩合。有机醇处理获得的木质素中,含有几乎等量的非缩合型愈创木基和紫丁香基结构单元及少量的对羟苯基结构单元。     

Biological variability in lignification of maize: Expression of the brown midrib bm2 mutation

The cell wall phenolic components in the internodes of three maize genotypes, namely normal, bm2 and bm3 maize, were determined. The bm2 and bm3 brown midrib mutations lowered the lignin content of the bottom, middle and top internodes to a similar extent. However, unlike bm3, the bm2 trait did not induce a sharp reduction of the level of ester-bound p-coumaric acid in maize internodes. The other main alkali labile phenolic acid, ferulic acid, reached similar levels in the three genotypes. The main difference between bm2 and bm3 mutations occurred in the alkyl aryl ether linked structures of the lignin component. In contrast to bm3 lignins, which are characterised by a low syringyl content, the bm2 lignin had a lower content of guaiacyl units than lignin of normal maize internode. Consequently, the syringyl/guaiacyl molar ratio of bm2 lignin gave higher values (2.7–3.2) than those from either normal (0.9–1.5) or bm3 lignins (0.3). The alkali solubility of lignin was also compared between the three genotypes. Incorporation of the bm3 trait in maize led to a high recovery of alkali soluble lignin whereas the bm2 lignin had a similar solubility to the normal one in 2 M NaOH. The monomeric composition of the alkali soluble lignins was consistent with the non-condensed structures of the in-situ polymer. Although the bm3 and bm2 mutations had different effects on lignification, the modification of the cell wall phenolic level was also found in the bm2 maize stem as previously studied.     

木素和碳水化合物化学结构对硫酸盐法制浆工艺及生物燃料生产的影响

大多数研究将重点放在认识单个木材组分的行为上,其目的旨在确定阔叶木材脱木素和碳水化合物的降解。这些研究倾向于测定脱木素速率或碳水化合物降解速率,但没有考虑某些相关变量引起的潜在相互影响。本文详细研究了大多数阔叶木材硫酸盐法制浆时木素和碳水化合物的降解过程,并测得桉木、山腊梅、蓝桉、枫香树、枫树、红橡树、红桤木、杨木和合欢树的脱木素速率;同时还研究了这些材种在主要脱木素阶段葡聚糖、聚木糖和总碳水化合物的溶解动力学。脱木素速率与碳水化合物的降解速率变化范围较大,与木材化学特性有关。结果表明,阔叶木硫酸盐制浆性能的差异主要受紫丁香基与愈疮木基比率和木素碳水化合物复合体（LCC）的影响。     

Characterisation of Lignin from Parenchyma and Sclerenchyma Cell Walls of the Maize Internode

Internodes of maize (Zea mays L, Co125), harvested 5 days after anthesis, were sectioned into five equal parts and samples of sclerenchyma and parenchyma cells mechanically isolated from each section. Phenolic acids and syringyl and guaiacyl degradation products of lignin were released from the walls of the two cell types by microwave digestion with 4 M NaOH. Aryl ether bonded units were selectively released by thioacidolysis. Total phenolic content of cell walls from the youngest (basal) sections were approximately two-thirds of those of the oldest, topmost sections (parenchyma 70·8–99·0 and sclerenchyma 72·5–114·1 mg g^-1) indicating that the process of lignification was already well advanced amongst most of the cell walls of the youngest section. The total phenolic content was marginally, but significantly, greater (P<0·05) in sclerenchyma walls than in parenchyma walls at all stages of maturity. There was no significant difference in phenolic acid concentrations between cell types from the same section but p-coumaric acid concentration increased with maturity (P<0·001) in walls from both cell types. The increase in p-coumarate with age was matched by an increased recovery of syringyl units resulting in a constant coumaroyl: syringyl molar ratio. Recovery of acetosyringone was significantly greater (P<0·001) from sclerenchyma than parenchyma walls and, in sclerenchyma, acetosyringone as a proportion of total syringyl recovery, increased significantly with age (P=0·015). Digestion with NaOH and thioacidolysis released comparable amounts of guaiacyl residues but NaOH digestion released approximately twice the amount of syringyl residues. This difference may be explained by the retention of the ester-bond between p-coumaric acid and syringyl units during thioacidolysis but not during digestion with 4 M alkali. The similarity in phenolic composition suggested that both cell types, despite their considerable anatomical differences, were exposed to a common flux of lignin precursors during the later stages of lignification as illustrated by the internode sections. Differences between cell walls arose because of differences in the regiochemistry of precursor incorporation. © 1997 SCI.