Measurement of emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood

Organic compound emission rates for volatile organic compounds (VOC), gas-phase semivolatile organic compounds, and particle-phase organic compounds are measured from residential fireplace combustion of wood. Firewood from a conifer tree (pine) and from two deciduous trees (oak and eucalyptus) is burned to determine organic compound emissions profiles for each wood type including the distribution of the alkanes, alkenes, aromatics, polycyclic aromatic hydrocarbons (PAH), phenol and substituted phenols, guaiacol and substituted guaiacol, syringol and substituted syringols, carbonyls, alkanoic acids, resin acids, and levoglucosan. Levoglucosan is the major constituent in the fine particulate emissions from all three wood types, contributing 18-30% of the fine particulate organic compound emissions. Guaiacol (2-methoxyphenol), and guaiacols with additional substituents at position 4 on the molecule, and resin acids are emitted in significant quantities from pine wood combustion. Syringol (2,6-dimethoxyphenol) and syringols with additional substituents at position 4 on the molecule are emitted in large amounts from oak and eucalyptus firewood combustion, but these compounds are not detected in the emissions from pine wood combustion. Syringol and most of the substituted syringols are found to be semivolatile compounds that are present in both the gas and particle phases, but two substituted syringols that have not been previously quantified in wood smoke emissions, propionylsyringol and butyrylsyringol, are found exclusively in the particle phase and can be used to help trace hardwood smoke particles in the atmosphere. Benzene, ethene, and acetylene are often used as tracers for motor vehicle exhaust in the urban atmosphere. The contribution of wood smoke to the ambient concentrations of benzene, ethene, and acetylene could lead to an overestimate of the contribution of motor vehicle tailpipe exhaust to atmospheric VOC concentrations.     

Phosphoric Acid-assisted Pretreatment Strategy for the Rational Synthesis of Lignin-derived Hierarchical Porous Carbon Toward High-performance Supercapacitors

In this article, a facile two-step activation method, coupled with phosphoric acid (H₃PO₄)-assisted pretreatment and followed KOH activation, was reported for constructing hierarchical porous carbon (HPC) materials derived from lignin. The introduction of H₃PO₄, cross-linked with lignin sources generated phosphate (and/or polyphosphate) ester groups throughout the lignin structure, which endowed the pre-activated intermediate char (IC) with a hierarchical porous structure. Such phosphate esters contributed to the multi-scale pore structure within the pre-activated IC, which was beneficial for the uniform distribution and impregnation of subsequent KOH activators, thus leading to the formation of HPC materials. The as-prepared HPC exhibited a large specific surface area (SSA) of 1345.1 m²/g, which ensures the accessibility of the ion diffusion pathways. The supercapacitors integrated with HPC delivered a high specific capacitance of 241 F/g (in a three-electrode system) and outstanding rate capability with an 80.9% capacitance retention from 0.5 A/g to an ultra-high current density of 50 A/g.     

Exposure of grapes to smoke of vegetation with varying lignin composition and accretion of lignin derived putative smoke taint compounds in wine

Smoke taint in wines from bushfire smoke exposure has become a concern for wine producers. Smoke taint compounds are primarily derived from pyrolysis of the lignin component of fuels. This work examined the influence of the lignin composition of pyrolysed vegetation on the types of putative smoke taint compounds that accrue in wines. At veraison, Merlot vines were exposed to smoke generated from five vegetation types with differing lignin composition. Smoke was generated under pyrolysis conditions that simulated bushfire temperature profiles. Lignin and smoke composition of each fuel type along with putative smoke taint compounds in wines were determined. The results showed that, regardless of fuel type, the commonly reported guaiacyl lignin derived smoke taint compounds, guaiacol and 4-methylguaiacol, represented about 20% of the total phenols in wines. Quantitatively, syringyl lignin derived compounds dominated the total phenol pools in both free and bound forms. The contributions of p-hydroxyphenyls were generally similar to the guaiacyl sources. A further unexpected outcome of the study was that pine smoke affected wines had significantly elevated levels of syringols compared to the controls although pine fuel and its smoke emission lacked syringyl products.     

低共熔溶剂提取天然产物的研究进展

低共熔溶剂(deep eutectic solvent,DES)作为绿色溶剂在天然产物提取方面具有巨大的应用潜力。本文对DES在黄酮类、木质素类、酚类、生物碱类、多糖类、挥发油类等提取中的应用进行综述,以期为DES在天然产物提取方面的应用提供参考。     

Changes in wood extractives from oak cask staves through maturation of scotch malt whisky

Cask staves, prepared from American white oak, Quercus alba, were obtained from unused, new charred Bourbon, used Bourbon, first-fill Scotch and exhausted Scotch casks. The aim of the experiment was to determine the effect of repeated maturations of whisky on concentration and location of phenolic extractives in the cask wood. Contents of vanillic and syringic acids and the respective aldehydes, arising from hydrolysis of guaiacyl-syringyl lignin, and whisky lactones (cis- and trans-β-methyl-γ-octalactone), arising from charring, were determined. Staves were sampled at 5 mm intervals from the inner char surface to 25 mm depth and wood extracted with chloroform, heptane and aqueous ethanol. Contents of material absorbing at 520 nm, total phenols and vanillic and syringic acids, vanillin and syringaldehyde, were determined by high-performance liquid chromatography; both isomers of whisky lactone were quantified by high-resolution gas chromatography. New cask wood had a maximum for coloured material in the char layer, but maxima for other compounds at 5 mm below the char. As casks were reused in maturations of whiskies, the contents of aromatic aldehydes and acids were reduced in the first 20 mm of the wood and maxima for both acids and aldehydes shifted towards the centre of the staves. This suggested that repeated exposure to aqueous ethanol resulted in compositional changes in the lignin in the wood. The newly charred wood had a maximum for cis-β-methyl-γ-octalactone at 5 mm below the char and the trans isomer at 15 mm. In the first Bourbon maturation both isomers were largely depleted and with successive extractions the maxima moved into the cask until in the exhausted cask wood no lactone was detected.     

Effect of Extraction Procedures on Fluorescent Chromophores in Milk

The oxidation of membrane lipids of freeze-dried Milk Fat Globule Membranes (MFGM) was studied using a fluorescence technique involving two different extraction procedures to obtain lipophilic fluorescent chromophores. MFGM underwent extensive lipid oxidation when stored under air, at controlled temperature and humidity and fluorescent compounds were formed with excitation maxima at 350 nm and emission maxima at 440 nm. Direct extraction of fluorescent compounds with an organic solvent mixture (Cl₃CH:CH₃OH 2:1 v/v) gave reproducible results reflecting well the progress of oxidation. Solvent extraction after previous reconstitution (to original water content) of the dry samples was less satisfactory.     

Systematische Untersuchungen der Wirkung aggressiver Gase auf Fichtenholz

In part 2 the effects of the aggressive gases formaldehyde, ammonia, sulfur dioxide and chlorine on lignin and polysaccharides in spruce wood are described. Formaldehyde causes no degradation of lignin and only minor changes in the polysaccharides. The degradation of lignin by NH₃, SO₂ and Cl₂ is increased in varying degrees by a high water content. The cell wall swelling during NH₃ treatment improves the alkali solubility of polyoses. The cellulose structures are attacked at their surfaces by NH₃, SO₂ hydrolytically cleaves polyoses and less ordered cellulose. Chlorine also penetrates the cellulose structures and causes intensive degradation. A high water content of the wood samples impedes this degrading effect of chlorine.     

生物活性多甲氧基黄酮羧酸和氨基酸衍生物的合成及其结构表征

多甲氧基黄酮(PMFs)是一类存在于柑橘属植物中具有显著抗癌、抗炎和抗氧化等生物活性的天然产物。为了提高多甲氧基黄酮类化合物的水溶性和药用价值,以2种来源丰富且抗癌活性高的多甲氧基黄酮橘皮素和川陈皮素为底物,分别经过氧丙酮氧化得到多甲氧基黄酮醇[3-羟基橘皮素(7)和3-羟基川陈皮素(8)],化合物7和化合物8分别在K₂CO₃和N,N-二甲基甲酰胺条件下与氯乙酸乙酯进行Williamson反应,生成了多甲氧基黄酮羧酸酯类衍生物,再经碱性水解合成了2种未见文献报道的多甲氧基黄酮羧酸衍生物[橘皮素-3-O-乙酸(1)和川陈皮素-3-O-乙酸(2)]。化合物1和化合物2在CH₂Cl₂作溶剂、1-(3-二甲基丙胺)-3-乙基碳二亚胺盐酸盐为缩合剂和4-N,N-二甲氨基吡啶为辅助剂的条件下,分别与2种不同的氨基酸甲酯盐酸盐发生缩合反应,得橘皮素和川陈皮素的氨基酸甲酯衍生物,然后经水解反应得到了4种新型多甲氧基黄酮氨基酸衍生物3～6。对所合成的化合物用¹H NMR、¹³C NMR和MS等方法进行了结构表征。     

Short-term methane emissions from 2 dairy farms in California estimated by different measurement techniques and US Environmental Protection Agency inventory methodology: A case study

Reported estimates of CH₄ emissions from ruminants and manure management are up to 2 times higher in atmospheric top-down calculations than in bottom-up (BU) inventories. We explored this discrepancy by estimating CH₄ emissions of 2 dairy facilities in California with US Environmental Protection Agency (US EPA) methodology, which is used for BU inventories, and 3 independent measurement techniques: (1) open-path measurements with inverse dispersion modeling (hereafter open-path), (2) vehicle measurements with tracer flux ratio method, and (3) aircraft measurements with the closed-path method. All 3 techniques were used to estimate whole-facility CH₄ emissions during 3 to 6 d per farm in the summer of 2016. In addition, open-path was used to estimate whole-facility CH₄ emissions over 13 to 14 d per farm in the winter of 2017. Our objectives were to (1) compare whole-facility CH₄ measurements utilizing the different measurement techniques, (2) compare whole-facility CH₄ measurements to US EPA inventory methodology estimates, and (3) compare CH₄ emissions between 2 dairies. Whole-facility CH₄ estimates were similar among measurement techniques. No seasonality was detected for CH₄ emissions from animal housing, but CH₄ emissions from liquid manure storage were 3 to 6 times greater during the summer than during the winter measurement periods. The findings confirm previous studies showing that whole-facility CH₄ emissions need to be measured throughout the year to estimate and evaluate annual inventories. Open-path measurements for liquid manure storage emissions were similar to monthly US EPA estimates during the summer, but not during the winter measurement periods. However, the numerical difference was relatively small considering yearly emission estimates. Manure CH₄ emissions contributed 69 to 79% and 26 to 47% of whole-facility CH₄ emissions during the summer and winter measurement periods, respectively. Methane yields from animal housing were similar between farms (on average 20.9 g of CH₄/kg of dry matter intake), but CH₄ emissions normalized by volatile solids (VS) loading from liquid manure storage (g of CH₄ per day/kg of VS produced by all cattle per day) at 1 dairy were 1.7 and 3.5 times greater than at the other during the summer (234 vs. 137 g of CH₄/kg of VS) and winter measurement periods (78 vs. 22 g of CH₄/kg of VS), respectively. We attributed much of this difference to the proportion of manure stored in liquid (anaerobic) form, and suggest that manure management practices that reduce the amount of manure solids stored in liquid form could significantly reduce dairy CH₄ emissions.     

Characterization of trembling aspen wood (Populus tremuloides L.) degraded with the white rot fungus Ceriporiopsis subvermispora and MWLs isolated thereof

Trembling aspen wood (Populus tremuloides L.) was treated with white rot fungus Ceriporiopsis subvermispora for 1, 2, 4, and 6 weeks. As fungal decay advanced, lignin contents were decreased gradually up to ca. 27.5% (based on the Klason residues of the control) after 6 weeks. Alkali solubility of cell wall residues was increased until 4 weeks of fungal treatment, but additional treatment did not cause any effects. Milled wood lignins (MWLs) were isolated from the decayed woods by Björkman’s procedure and subjected to thioacidolysis and analytical pyrolysis to investigate the modification of lignin structures during fungal degradation. Thioacidolysis revealed that the yields of trithioethylated C₆C₃ monomers, as a parameter for frequency of β-O-4 linkages in lignin, were substantially reduced (-20%, based on the control) in MWLs isolated from decayed woods. Analytical pyrolysis revealed that the relative amounts of coniferyl alcohol and sinapyl alcohol in the pyrolysates were lowered dependent on the biodegradation time, whereas an elevation of C₆C₁ and C₆C₂ pyrolytic phenols was observed. The results from both analytical methods strongly suggested that β-O-4 linkages were cleaved by C. subvermispora. Specially, degradation of syringyl-type lignin seems to be preferred.     

Fate of Singrin in Methanol/Ammonia/Water-Hexane Extraction of B. juncea Mustard Seed

The individual glucosinolates present in B. juncea mustard seed were determined. Sinigrin (allyl glucosinolate) was the major glucosinolate of mustard seed and constituted 92.9% of the total glucosinolates. The effect of CH₃OH/NH₃/H₂O-hexane treatment on the concentration of glucosinolates was studied. Over 97% of sinigrin originally present in the seed was removed by the above solvent extraction system, mainly in the intact form. Breakdown products of sinigrin were quantified in the treated meal, in the extracted oil and in the polar phase (gums). Aglycon products were allyl cyanide, allyl isothiocyanate and 2,3-epithiopropane cyanide. Sugar breakdown products were glucose, thioglucose, thioglucose dimer and furfuryl alcohol. Desulfosinigrin was a minor decomposition product and might have acted as an intermediate in the decomposition of sinigrin.     

活性炭吸附结合TiO2光催化分离纯化杨木预水解液中的木糖

利用活性炭吸附和TiO₂光催化降解脱除杨木预水解液中的溶解木素,探讨了不同活性炭类型（木质基磷酸活化活性炭、食品质303活性炭、煤质活性炭）、活性炭用量、吸附时间、光催化时间、TiO₂用量对预水解液中木素、总木糖、糠醛、羟甲基糠醛（5-HMF）以及乙酸等有机组分含量的影响,优化确定了活性炭吸附和TiO₂光催化降解条件。研究结果表明,木质基磷酸活化活性炭对木素的吸附脱除效果最好,在活性炭用量为1.0%和吸附时间为10 min时,总木糖得率为93.1%,木素、糠醛、5-HMF、乙酸脱除率分别为75.1%、29.3%、22.4%、3.5%。单一TiO₂光催化处理,在TiO₂用量1.0%和光催化时间10 h条件下,总木糖得率为89.0%,木素、糠醛、5-HMF、乙酸脱除率分别为40.2%、24.2%、32.1%、3.1%。活性炭协同TiO₂光催化处理预水解液的较优工艺条件为：木质基磷酸活化活性炭用量1.0%、光催化时间6 h和TiO₂用量0.1%~0.5%,此条件下预水解液中木素的脱除率为84.4%~86.7%,总木糖得率为88.2%~89.8%,糠醛脱除率为53.8%~65.1%,5-HMF脱除率为48.6%~51.7%,乙酸含量变化不明显 。     

利用多酚/蛋白互作模型研究多酚对葡萄酒涩感的影响

研究不同红葡萄酒中不同聚合度的酚类物质与蛋白质相互作用的差异性,找出影响涩感的关键成分,为葡萄酒酿造工艺的改良及葡萄品种的选育提供理论依据。以不同品种的红葡萄酒为材料,利用C18固相萃取柱将葡萄酒的酚类物质分离为单体酚、低聚物、高聚物三部分,测定其总酚、总黄烷醇含量,采用SDS-PAGE及荧光光谱法研究不同酚类物质与蛋白质的相互作用。测得红葡萄酒的总酚和总黄烷醇含量存在显著差异,红葡萄酒中不同组分的总酚和总黄烷醇含量表现为:单体酚低聚物高聚物。SDS-PAGE及荧光光谱实验的结果显示高聚物对蛋白质的影响较强,单体酚与低聚物则因酒而异。葡萄酒中不同聚合度的成分对涩感的影响不同。因此,在葡萄品种选择和葡萄酒酿造工艺改良的过程中可以根据目标而进行酚类物质的控制,特别是高聚物的调控。     

Chemical characterisation of vegetable and arable crop residue materials: a comparison of methods

Although it is widely recognised that chemical composition controls the patterns of decomposition and N mineralisation of crop residue materials, there has been little agreement as to the nature of the most important chemical fractions. We investigated whether this could be attributed to differences in methodologies employed for chemical characterisation of the lignin and cellulose fractions of plant materials. The cellulose and lignin contents of cauliflower, potato, red beet, Brussels sprouts and wheat crop residues were analysed by a number of contrasting methods. These were forage fibre and forest products analyses, which utilise KMnO₄ and H₂SO₄ respectively to separate the two fractions, and a third method, which employs NaClO₂. For all the materials, the forage fibre method gave substantially lower amounts of both lignin and cellulose than the other methods. There was correlation between lignin determined by the different methods. Low recovery of lignin by the forage fibre method was found to arise partly from incomplete delignification by KMnO₄. The cellulose contents given by the different methods were highly correlated. However, it was apparent that the forage fibre method underestimated cellulose, since only alpha-cellulose was measured. The characteristics of crop residues grown on two sites with different N fertiliser treatments were determined by forest products analysis. The materials were shown to span a range with respect to both lignin (12–26%) and cellulose (17–71%) contents. The chemical characteristics of the materials were not significantly affected by the amount of nitrogen used to produce the crop. © 1999 Society of Chemical Industry     

黑液快速热解工艺及实验

在无氧环境下对黑液进行快速热解,获得液态的生物油和由碱金属盐类与炭结合组成的焦炭。结果表明:黑液快速热解将黑液中的木素转化为含丰富的酚类化合物的生物油,有利于黑液的资源化利用;生物油的GC-MS分析表明,其主要由10种酚类、6种酮类及5种不饱和烃类组成,其中酚类相对百分含量高达88.02%,是代替苯酚合成酚醛树脂胶黏剂的理想原料;理论上可以通过快速热解高效回收碱。     

Effects of supercritical and liquid carbon dioxide extraction on hemp (Cannabis sativa L.) seed oil

The increase in the popularity of hemp-based products is mainly linked to the presence of non-psychoactive cannabinoids that provide relief from aches, pain and anxiety. In this study, hemp seed oils were produced by two innovative and environmentally friendly extraction techniques: supercritical and liquid carbon dioxide (CO₂) extraction. The chemical composition of the two oils was analysed and compared with that of a control oil obtained by solvent (n-hexane) extraction. Both oils obtained by liquid and supercritical CO₂ extraction presented interesting compositions: they contained large amounts of cannabinoids, polyphenols and tocopherols and were less oxidised than the control and contained a large amount of hexanal, which provided a pleasant aroma. The maximum cannabinoid content was found in the oil obtained by liquid CO₂ extraction (71.51 mg of cannabidiol per kg of oil and 113.92 mg of cannabinol per kg of oil). Carotenoids were prevalent in the oil obtained by supercritical CO₂ extraction (61.00 mg kg⁻¹ of oil).     

Prediction of methane production from dairy and beef cattle

Methane (CH₄) is one of the major greenhouse gases being targeted for reduction by the Kyoto protocol. The focus of recent research in animal science has thus been to develop or improve existing CH₄ prediction models to evaluate mitigation strategies to reduce overall CH₄ emissions. Eighty-three beef and 89 dairy data sets were collected and used to develop statistical models of CH₄ production using dietary variables. Dry matter intake (DMI), metabolizable energy intake, neutral detergent fiber, acid detergent fiber, ether extract, lignin, and forage proportion were considered in the development of models to predict CH₄ emissions. Extant models relevant to the study were also evaluated. For the beef database, the equation CH₄ (MJ/d) = 2.94 (± 1.16) + 0.059 (± 0.0201) × metabolizable energy intake (MJ/d) + 1.44 (± 0.331) × acid detergent fiber (kg/d) - 4.16 (± 1.93) × lignin (kg/d) resulted in the lowest root mean square prediction error (RMSPE) value (14.4%), 88% of which was random error. For the dairy database, the equation CH₄ (MJ/d) = 8.56 (± 2.63) + 0.14 (± 0.056) × forage (%) resulted in the lowest RMSPE value (20.6%) and 57% of error from random sources. An equation based on DMI also performed well for the dairy database: CH₄ (MJ/d) = 3.23 (± 1.12) + 0.81 (± 0.086) × DMI (kg/d), with a RMSPE of 25.6% and 91% of error from random sources. When the dairy and beef databases were combined, the equation CH₄ (MJ/d) = 3.27 (± 0.79) + 0.74 (± 0.074) × DMI (kg/d) resulted in the lowest RMSPE value (28.2%) and 83% of error from random sources. Two of the 9 extant equations evaluated predicted CH₄ production adequately. However, the new models based on more commonly determined values showed an improvement in predictions over extant equations.     

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     

Effect of Natural Extracted Antioxidants from Eriobotrya japonica (Lindl.) Fruit Skin on Thermo Oxidative Stability of Soybean Oil During Deep Frying

The effects of ultrasound-assisted, supercritical CO₂ and solvent extraction techniques on antioxidant activity of Eriobotrya japonica (Lindl.) skin extracts were investigated using 2, 2-diphenyl-1-picrylhydrazyl, β-carotene, and Rancimat assays. Solvent extract of skin at 400 ppm had the highest antioxidant activity. Solvent extraction was the most effective method on extraction of phenols and tocopherols. Protective effects of extracts in stabilization of soybean oil during frying were determined by measuring its peroxide value, total polar compounds, carbonyl value, free fatty acids, conjugated dienes, and trienes. Results indicated that solvent extract of skin at 400 ppm exhibited stronger antioxidant activity in oil than tertiary butylhydroquinone.     

Enhanced E/Z Isomerization of (All‐E)‐lycopene by Employing Iron(III) Chloride as a Catalyst

Catalytic isomerization of (all‐E)‐lycopene to Z‐isomers using iron(III) chloride was investigated and optimized under various conditions of solvents, concentrations of iron(III) chloride, and reaction temperatures. The total contents of Z‐isomers converted were higher in the order of CH₂Cl₂ (78.4%) > benzene (61.4%) > acetone (51.5%) > ethyl acetate (50.8%) at 20 °C for 3 h using 1.0 × 10^?3 mg/mL iron(III) chloride for 0.1 mg/mL (all‐E)‐lycopene. However, the decomposition of lycopene was markedly accelerated in CH₂Cl₂: the remaining lycopene after the reaction for 3 h and 12 h was only 79.4% and 47.5%, respectively. As the concentration of catalyst increased in acetone, the Z‐isomerization ratio of lycopene increased to more than 80%, followed by rapid degradation of lycopene to undetectable levels using >4.0 × 10^?3 mg/mL iron(III) chloride with the above concentration of (all‐E)‐lycopene. Finally, greater isomerization (79.9%) was attained at 60 °C in acetone for 3 h in the presence of 1.0 × 10^?3 mg/mL iron(III) chloride, largely without decomposition of lycopene (remaining ratio of total amount of lycopene isomers after the reaction, 96.5%). As iron(III) chloride has found general use as a food additive for iron fortification and acetone is also widely used in the food field, this method can be applied to the food and beverage processing industry.