Studies on the effect of ball milling on lignin structure using a modified DFRC method.

The structures of milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and residual lignin (REL) from a loblolly pine were analyzed using a modified derivatization followed by reductive cleavage (DFRC) method developed to allow the quantitative determination of three different structural monomeric products originating in lignin: phenolic beta-O-4, alpha-O-4, and etherified beta-O-4 structures. Results show that MWL and CEL are structurally identical, with an increased phenolic beta-O-4 content compared to that of the original Wiley milled wood. These results indicate that the portion of lignin linked to carbohydrates and that not linked to carbohydrates are structurally the same. Modified DFRC analysis of the effect of ball milling on the structure of lignin in wood, MWL, CEL, and REL indicate that vibratory ball milling does not change the lignin structure provided certain precautions are taken. Specifically, dry vibratory ball milling under a nitrogen atmosphere causes substantial structural changes including condensation, whereas vibratory ball milling in toluene had little effect on the lignin structure. This indicates that the structural differences observed in MWL and CEL arise because of the extraction procedure, which preferentially extracts phenolic lignin structures. MWL and CEL are representative of the total lignin in wood; however, due primarily to the solvent extraction process, higher phenolic hydroxyl contents are observed. Nitrobenzene oxidation showed structural results similar to those from the modified DFRC method.     

The DFRC method for lignin analysis. 7. Behavior of cinnamyl end groups.

The behavior of cinnamyl end groups of lignins during the derivatization followed by reductive cleavage (DFRC) procedure has been investigated using lignin model compounds. On AcBr treatment, hydroxycinnamyl alcohols give rise mainly to 1-aryl-1, 3-dibromopropanes from which 1-aryl-3-bromopropanes and arylcyclopropanes are formed by zinc reduction. Arylpropene derivatives are also significant among DFRC products of etherified cinnamyl end-group models. Major monomers from DFRC of hydroxycinnamaldehydes are arylcyclopropyl acetates produced by reductive ring closure of 1-acetoxy-3-aryl-1,3-dibromopropanes. Although the reactions are not as clean as the ether-cleaving reactions that form the basis of the DFRC method, end groups produce diagnostic compounds that provide valuable markers for studying end groups in lignins.     

Accuracy of Klason lignin and acid detergent lignin methods as assessed by bomb calorimetry.

An accurate method for estimation of lignin concentration is important for prediction of the digestible energy content of livestock feeds. The accuracy of lignin concentration estimates based on the Klason lignin and acid detergent lignin methods was compared. Ten diverse forage samples were analyzed for protein, carbohydrates, lipids, organic acids, ash, lignin (by both methods), and gross energy. The accuracy of the two lignin concentration estimates was examined by comparing the measured forage gross energy to a gross energy value calculated from the compositional analysis. Use of the acid detergent lignin estimate in this gross energy calculation accounted for 68-84% of the forage gross energy compared to 85-97% of the gross energy using Klason lignin. These results indicate that while Klason lignin estimates are substantially higher than acid detergent lignin estimates, Klason lignin is the more accurate lignin method and does not overestimate lignin because gross energy recoveries were less than 100%.     

Estimation and analysis of soil hydraulic properties through infiltration experiments: comparison of BEST and DL fitting methods

The BEST method (Beerkan estimation of soil transfer parameters through infiltration experiments) appears promising and easy to estimate not only saturated hydraulic conductivity but also water retention and hydraulic characteristics. However, few tests have been conducted to test the methodology. This study involved field BEST infiltration experiments for three layers (surface, 15 and 30 cm) for each of three soils with different soil textures under grassland. By comparing BEST with DL (differentiated linearization method), we found that the DL method did not produce a good estimate of the soil hydraulic properties and neither did it identify the transient flow state. The BEST method resulted in reasonable results and is therefore promising. However, with BEST we encountered some anomalies when calculating hydraulic properties in some cases with too few data points under the transient flow state. We show that the application of BEST field experiments requires a wide range of soil water content from initial to saturated states so as to include sufficient transient flow. The soil hydraulic properties determined using the BEST method showed contrasting characteristics between different soil textures with higher saturated hydraulic conductivity under coarse texture and lower values under loam textures, especially with highly compacted soils. Vertical variation in soil hydraulic properties was significant, and the surface layer had a lower saturated hydraulic conductivity partly caused by compaction (high bulk density) or by remnants of grass plants. Further research on the effects of compaction and grass plants on soil hydraulic properties is needed.     

Syntheses of lignin-derived thioacidolysis monomers and their uses as quantitation standards

Analytical thioacidolysis releases diagnostic monomers from lignins by selectively cleaving alkyl aryl ether bonds. High yielding syntheses of the three thioacidolysis monomers were developed, and the compounds were used as standards for gas chromatography-mass spectrometry (GC-MS) and gas chromatography-flame ionization detector (GC-FID) quantitation of monomers released from lignocellulosics. First, syringyl, guaiacyl, and p-hydroxyphenyl glycerols were synthesized from the corresponding ethyl cinnamates and used as thioacidolysis substrates to prepare the monomers in high yields. These monomers were then used as standard compounds to measure their GC-MS and GC-FID response factors against two internal standards, 4,4'-ethylenebisphenol and tetracosane. For quantitation, it was shown that 4,4'-ethylenebisphenol is the better internal standard for GC-MS, whereas tetracosane remains the choice for GC-FID. When the obtained response factors were applied, the thioacidolysis monomer yields from white spruce, loblolly pine, poplar, bamboo, and sugar cane bagasse were determined by GC-MS. The obtained results were consistent with those reported in the literature.     

Organosolv ethanol lignin from hybrid poplar as a radical scavenger: relationship between lignin structure, extraction conditions, and antioxidant activity

Twenty-one organosolv ethanol lignin samples were prepared from hybrid poplar (Populus nigra xP. maximowiczii) under varied conditions with an experimental matrix designed using response surface methodology (RSM). The lignin preparations were evaluated as potential antioxidants. Results indicated that the lignins with more phenolic hydroxyl groups, less aliphatic hydroxyl groups, low molecular weight, and narrow polydispersity showed high antioxidant activity. Processing conditions affected the functional groups and molecular weight of the extracted organosolv ethanol lignins, and consequently influenced the antioxidant activity of the lignins. In general, the lignins prepared at elevated temperature, longer reaction time, increased catalyst, and diluted ethanol showed high antioxidant activity. Regression models were developed to enable the quantitative prediction of lignin characteristics and antioxidant activity based on the processing conditions.     

Inhomogeneities in the chemical structure of sugarcane bagasse lignin

Sequential treatments of dewaxed bagasse with distilled water, 0.5 M NaOH, 0.5, 1.0, 1.5, 2.0, and 3.0% H(2)O(2) at pH 11.5, and 2 M NaOH at 55 degrees C for 2 h solubilized 2.8, 52.5, 14.9, 3.3, 5.5, 5.0, 2.8, and 2.2% of the original lignin, respectively. The eight isolated lignin fractions were subjected to a comprehensive structural characterization by UV, FT-IR, and (1)H and (13)C NMR spectroscopies and thermal analysis. The nitrobenzene oxidation method was also applied to the in situ lignins. The seven lignin fractions, isolated successively with alkali and alkaline peroxide, were all SGH-type lignins, with a small amount of esterified p-coumaric acid and mainly etherified ferulic acid. No significant differences were found in the weight-average molecular weights (1680-2220 g/mol) of the seven alkali and alkaline peroxide dissolved lignins. However, the first four lignin fractions, isolated with 0.5 M NaOH and 0.5, 1.0, and 1.5% H(2)O(2) at pH 11.5, were rich in syringyl units and contained large amounts of noncondensed ether structures, whereas the last three lignin fractions, isolated sequentially with 2.0 and 3.0% H(2)O(2) at pH 11.5 and 2 M NaOH at 55 degrees C for 2 h, had a higher degree on condensation and were rich in guaiacyl lignins.     

Combined methods for the determination of lignin and cellulose in leaf litter

Precise and specific methods for the simultaneous quantitative determination of lignin and cellulose are discussed in this paper, enabling the monitoring of even slight changes in the content of lignocellulose in dead plant material during decomposition processes. Results from different leaf litter samples as well as a comparison of the lignocellulose content of freshly fallen leaf litter, leached and microbially inoculated leaf litter, and feces of saprophagous soil animals fed on this food source are presented. The suitability of the described methods for investigating decomposition processes is discussed.     

木质素改性产物对钾肥的缓释作用与作物吸钾量的影响

利用木质素改性产物作为肥料添加剂 ,与氯化钾复混制成木质素钾肥 ,通过土柱淋溶与盆栽试验 ,验证木质素对钾肥的缓释作用与作物对钾肥利用情况。结果表明 ,木质素不仅可以减少钾肥流失 ,而且可以促进番茄与玉米生长 ,提高作物对钾的吸收。木质素来源于造纸废液 ,作为钾肥的缓释材料 ,其资源环保意义重大。     

Comparison of the acetyl bromide spectrophotometric method with other analytical lignin methods for determining lignin concentration in forage samples

Present analytical methods to quantify lignin in herbaceous plants are not totally satisfactory. A spectrophotometric method, acetyl bromide soluble lignin (ABSL), has been employed to determine lignin concentration in a range of plant materials. In this work, lignin extracted with acidic dioxane was used to develop standard curves and to calculate the derived linear regression equation (slope equals absorptivity value or extinction coefficient) for determining the lignin concentration of respective cell wall samples. This procedure yielded lignin values that were different from those obtained with Klason lignin, acid detergent acid insoluble lignin, or permanganate lignin procedures. Correlations with in vitro dry matter or cell wall digestibility of samples were highest with data from the spectrophotometric technique. The ABSL method employing as standard lignin extracted with acidic dioxane has the potential to be employed as an analytical method to determine lignin concentration in a range of forage materials. It may be useful in developing a quick and easy method to predict in vitro digestibility on the basis of the total lignin content of a sample.     

Characterization of dietary fiber lignins from fruits and vegetables using the DFRC method

Insoluble fiber fractions from 11 fruits and vegetables were investigated for their lignin composition using the derivatization followed by reductive cleavage (DFRC) methodology. To enrich lignin contents and to minimize polysaccharide excess that led to nonanalyzable DFRC chromatograms, the insoluble fibers were degraded by a carbohydrolases mixture. The residues that were found to be representative for the insoluble fiber lignins were analyzed. The investigated fibers differ considerably in their lignin contents and also in their lignin compositions. With the exception of radish fiber, only trace amounts (or none) of the products resulting from p-hydroxyphenyl units were detected. Lignins noticeably differed in the ratio of the DFRC products resulting from syringyl units (S) and guaiacyl (G) units (G/S ratios ranged from approximately 39 to 0.2). The insoluble fiber lignins were classified as G-rich lignins (G/S ratio > 3; carrot, spinach, kiwi, curly kale, radish, and asparagus), S-rich lignins (S/G ratio > 3; rhubarb), or balanced lignins (0.3 < G/S ratio < 3; pear, apple, small radish, and kohlrabi). Information about further structural characteristics, for example, cinnamyl endgroups, was obtained from the analysis of DFRC minor products.     

Determination of lactose in milk: comparison of methods

A new enzymatic method based on the spectrophotometric measurement of reduced NAD+ (beta-nicotinamide-adenine dinucleotide) at 340 nm has been evaluated by comparing it with the AOAC copper reduction method. Ten samples of milk containing various levels of lactose were analyzed in duplicate by the enzymatic method, and 5 samples were analyzed by the copper reduction method. Statistical analysis using a factorial design revealed no statistical significance between results obtained by the 2 methods; recoveries were comparable, 97% or greater for all except one sample. There was no relationship between amount of lactose added and percent recovered.     

Impact of lignin structure and cell wall reticulation on maize cell wall degradability

In this study, eight maize recombinant inbred lines were selected to assess both the impact of lignin structure and the impact of cell wall reticulation by p-hydroxycinnamic acids on cell wall degradability independently of the main "lignin content" factor. These recombinant lines and their parents were analyzed for in vitro degradability, cell wall residue content, esterified and etherified p-hydroxycinnamic acid content, and lignin content and structure. Lignin structure and esterified p-coumaric acid content showed significantly high correlation with in vitro degradability (r=-0.82 and r=-0.72, respectively). A multiple regression analysis showed that more than 80% of cell wall degradability variations within these 10 lines (eight recombinant inbred lines and their two parents) were explained by a regression model including two main explanatory factors: lignin content and estimated proportion of syringyl lignin units esterified by p-coumaric acid. This study revealed new biochemical parameters of interest to improve cell wall degradability and promote lignocellulose valorization.     

Phosphorus in wine: comparison of atomic absorption spectrometry methods

Phosphorus in wine may be determined directly or indirectly by atomic absorption spectrometry. The direct method uses the carbon rod atomizer as the excitation source and a phosphorus hollow cathode lamp. In the indirect determination, one measures the amount of molybdenum that will complex with phosphorus in the wine. Both nitrous oxide-acetylene and air-acetylene flames are suitable as atomization sources in this indirect method. The resultant data have been compared with those from the AOAC colorimetric method (11.032-11.034). A 2-sample comparison test showed the results to be insignificantly different at the 95% confidence limits.     

Determination of arylglycerol-beta-aryl ethers and other linkages in lignins using DFRC/(31)P NMR

An analytical method for lignins has been developed that involves derivatization followed by reductive cleavage (DFRC), depolymerization, and quantitative (31)P NMR spectroscopy. This technique detects and quantifies the various ether linkages present in softwood residual kraft lignins (RKL) and milled wood lignins (MWL). In addition, the technique supplies new quantitative information about beta-aryl ethers linked to condensed and noncondensed aromatic moieties, including dibenzodioxocins. Within RKL, beta-aryl ether bonds connected to condensed phenolic moieties predominated over those connected to noncondensed phenolic moieties. In addition, the amount of DFRC monomers determined by gas chromatography was minute in the RKL but large in the MWL. This indicates that almost all noncondensed beta-aryl ether linkages were cleaved during kraft pulping. The method offers new avenues for the detailed investigation of the bonding patterns of native and technical lignins.     

Soil degradative effects of slope length and tillage methods on alfisols in western Nigeria. III.Soil physical properties

Effects of six slope lengths, 60 m to 10 m with 10-m increments, on soil physical properties were evaluated for plough-based conventional till and no-till seedbed preparation on field runoff plots for three consecutive years from 1984 to 1987. Soil physical properties measured included texture, bulk density, infiltration capacity, and soil moisture retention characteristics. Conventional till treatment caused a rapid increase in soil bulk density and penetration resistance, and decrease in available water capacity and equilibrium infiltration rate. Gravel content increased with cultivation duration. Soil bulk density of 0–5 cm depth was 1·20 Mg m⁻³ for 1984, 1·39 Mg m⁻³ for 1985 and 1·46 Mg m⁻³ for 1986 for conventional till; and 1·13 Mg m⁻³ for 1984, 1·33 Mg m⁻³ for 1985, and 1·27 Mg m⁻³ for 1986 for the no-till treatment. The penetration resistance of the no-till treatment was relatively low and increased with cultivation duration. Mean penetration resistance for 0–5 cm depth was 2·2 kg cm⁻² in 1984, 2·71 kg cm⁻² in 1985, and 3·79 kg cm⁻² in 1986. The available water capacity decreased in both tillage methods without any consistent trends with regard to slope length. The equilibrium infiltration rate declined drastically for long slopes and conventional till methods. The data support the conclusion that these soils should be managed with short slope lengths and a no-till method of seedbed preparation. © 1997 John Wiley & Sons, Ltd.     

Estimating evaporation: A comparison between Penman, Idso-Jackson, and zero-flux methods

A field evaporation—drainage study was conducted to compare three methods of predicting evaporative losses from a bare soil. Two of the methods (modified Penman combination and Idso—Jackson) are dependent only on measurements of atmospheric parameters whereas the third method (plane of zero flux) is dependent only on measurements of soil parameters.A Captina soil profile was wet up and allowed to dry by evaporation and drainage. For the initial two days after infiltration ceased all three methods predicted similar evaporative losses. Differences between the three methods occurred when the soil moisture content at the soil surface controlled the evaporation rates. Under the three drying conditions the three methods behaved somewhat differently in the prediction of the amounts of water evaporated from the soil surface. Lower losses by evaporation were predicted by the Idso—Jackson and zero-flux methods. In the case of the Idso—Jackson method this result was attributed to the influence of clouds on albedo, the impact of wind and the importance of albedo in the predictive equation. For the zero-flux method the decrease in evaporation was due to lower soil water contents and matrix potentials near the surface which resulted in lower transport rates of water to the surface.     

Soil degradative effects of slope length and tillage methods on alfisols in Western Nigeria. I. Runoff,erosion and crop response

Field runoff plots were established in 1984 to evaluate the effects of slope length on runoff, soil erosion and crop yields on newly cleared land for four consecutive years (1984–1987) on an Alfisol at Ibadan, Nigeria. The experimental treatments involved six slope lengths (60 m to 10 m at 10-m increments) and two tillage methods (plough-based conventional tillage and a herbicide-based no-till method) of seedbed preparation. A uniform crop rotation of maize (Zea mays)/cowpeas (Vigna unguiculata) was adopted for all four years. An uncropped and ploughed plot of 25 m length was used as a control. The water runoff from the conventional tillage treatment was not significantly affected by slope length, but runoff from the no-till treatment significantly increased with a decrease in slope length. The average runoff from the no-till treatment was 1·85 per cent of rainfall for 60 m, 2·25 per cent for 40 m, 2·95 per cent for 30 m, 4·7 per cent for 20 m and 5·15 per cent for 10 m slope length. In contrast to runoff, soil erosion in the conventional tillage treatment decreased significantly with a decrease in slope length. For conventional tillage, the average soil erosion was 9·59 Mg ha⁻¹ for 60 m, 9·88 Mg ha⁻¹ for 50 m, 6·84 Mg ha⁻¹ for 40 m, 5·69 Mg ha⁻¹ for 30 m, 1·27 Mg ha⁻¹ for 20 m and 2·19 Mg ha⁻¹ for 10 m slope length. Because the no-till method was extremely effective in reducing soil erosion, there were no definite trends in erosion with regard to slope length. The average sediment load (erosion:runoff ratio) also decreased with a decrease in slope length from 66·3 kg ha⁻¹ mm⁻¹ for 60 m to 36·3 kg ha⁻¹ mm⁻¹ for 10 m slope length. The mean C factor (ratio of soil erosion from cropped land to uncropped control) also decreased with a decrease in slope length. Similarly, the erosion:crop yield ratio decreased with a decrease in slope length, and the relative decrease was more drastic in conventional tillage than in the no-till treatment. The slope length (L) and erosion relationship fits a polynomial function (Y=c+aL+bL²). Formulae are proposed for computing the optimum terrace spacing in relation to slope gradient and tillage method. © 1997 John Wiley & Sons, Ltd.