Lignin signature of subalpine Rendzinas (Tangel- and Moderrendzina) in the Bavarian Alps

Simple phenolic lignin degradation products released from alkaline CuO oxidation are used to characterize the lignin component of a Tangelrendzina and a Moderrendzina. The sum of CuO oxidation products describes the overall lignin decomposition pattern. The ratio of acid/aldehyde of the vanillyl unit and the ratio of syringyl/vanillyl units give an indication of the alteration of the remnant lignin molecule. In both soils the sum of lignin oxidation products shows a pronounced decrease with depth. In the Oh, Ca horizon of the Tangelrendzina and the Ah of the Moderrendzina an accumulation of lignin-derived phenolic compounds is observed. The strong increase of the acid/aldehyde ratio at the transition from the humus to the mineral horizons in both soils and the decrease of the syringyl/vanillyl ratio in the Moderrendzina demonstrate a considerable chemical alteration of the remnant lignin molecule (oxidation of side-chain, enrichment with vanillyl units) with progressive decomposition and humification of litter material. The depth functions of the lignin parameters are influenced by decomposition of lignin, accumulation of water-soluble lignin fragments and the input of root litter.     

Chemical characterization of lignin and lipophilic fractions from leaf fibers of curaua (Ananas erectifolius)

The chemical composition of leaf fibers of curaua (Ananas erectifolius), an herbaceous plant native of Amazonia, was studied. Special attention was paid to the content and composition of lignin and lipophilic compounds. The analysis of lignin in the curaua fibers was performed in situ by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and showed a lignin composition with a p-hydroxyphenyl:guaiacyl:syringyl units (H:G:S) molar proportion of 30:29:41 (S/G molar ratio of 1.4). The presence of p-hydroxycinnamic acids (p-coumaric and ferulic acids) in curaua fibers was revealed upon pyrolysis in the presence of tetramethylammonium hydroxide. On the other hand, the main lipophilic compounds, analyzed by GC/MS, were series of long-chain n-fatty acids, n-fatty alcohols, alpha- and omega-hydroxyacids, monoglycerides, sterols, and waxes. Other compounds, such as omega-hydroxy monoesters and omega-hydroxy acylesters of glycerol, were also found in this fiber in high amounts.     

Chemical characterization of lignin and lipid fractions in industrial hemp bast fibers used for manufacturing high-quality paper pulps

The chemical composition of lignin and lipids of bast fibers from industrial hemp (Cannabis sativa) used for high-quality paper pulp production was studied. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) of fibers showed a lignin with a p-hydroxyphenyl:guaiacyl:syringyl unit (H:G:S) molar proportion of 13:53:34 (S/G ratio of 0.64). p-Hydroxycinnamic acids, namely, p-coumaric and ferulic acids, were found in only trace amounts. Among the lipids, the main compounds identified by GC/MS of the hemp fibers extracts were series of n-alkanes, free and esterified sterols and triterpenols, waxes, and long-chain n-fatty acids. Other compounds such as n-aldehydes, n-fatty alcohols, steroid hydrocarbons, and steroid and triterpenoid ketones as well as steryl glycosides were also found.     

Chemical composition of abaca (Musa textilis) leaf fibers used for manufacturing of high quality paper pulps

The chemical composition of leaf fibers of abaca (Musa textilis), which are commonly used for high-quality paper pulp production, was thoroughly studied. The results revealed that the lignin content was 13.2% of the total fiber. The analysis of abaca fibers by pyrolysis coupled to gas chromatography-mass spectrometry (Py-GC/MS) released predominantly compounds arising from lignin and p-hydroxycinnamic acids, with high amounts of 4-vinylphenol. The latter compound was demonstrated to arise from p-coumaric acid by pyrolysis of abaca fibers in the presence of tetramethylammonium hydroxide, which released high amounts of p-coumaric acid (as the methyl derivative). Products from p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) propanoid units, with a predominance of the latter (H:G:S molar ratio of 1.5:1:4.9), were also released after Py-GC/MS of abaca fibers. Sinapyl and coniferyl acetates, which are thought to be lignin monomer precursors, were also found in abaca. The extractives content of the abaca fiber (0.4%) was low, and the most predominant compounds were free sterols (24% of total extract) and fatty acids (24% of total extract). Additionally, significant amounts of steroid ketones (10%), triglycerides (6%), omega-hydroxyfatty acids (6%), monoglycerides (4%), fatty alcohols (4%), and a series of p-hydroxycinnamyl (p-coumaric and ferulic acids) esterified with long chain alcohols and omega-hydroxyfatty acids were also found, together with minor amounts of steroid hydrocarbons, diglycerides, alpha-hydroxyfatty acids, sterol esters, and sterol glycosides.     

Quantitative determination of hydroxycinnamic acids in wheat, rice, rye, and barley straws, maize stems, oil palm frond fiber, and fast-growing poplar wood.

A new method has been developed for the quantitative determination of hydroxycinnamic acids participating in ester or ether linkages to the cell wall polymers. The method is based on mild alkaline hydrolysis followed by acid hydrolysis or mild alkaline hydrolysis, which partially removed esterified phenolic acids, and high-temperature concentrated alkaline treatment, which cleaved both the ester and ether linkages. It was found that traditional mild alkaline hydrolysis and acid hydrolysis released only part of the ester- and ether-linked phenolic acids, respectively. Approximately half (44.0-47.9%) of the total ester-linked p-coumaric acid and 18.2-32.6% of the total esterified ferulic acid remained ester-linked to the mild alkali-soluble lignin polymers, and 55.0-72.0% of the total ether-linked p-coumaric acid and 37.5-53.8% of the total ether-linked ferulic acid remained ether-linked to the solubilized lignin molecules after the acid hydrolysis. To correct this, a second mild alkaline hydrolysis of the alkali-soluble lignin preparations and acid hydrolysis of the solubilized lignin fractions, obtained from the first acid hydrolysis of the cell wall materials, was investigated. On the basis of this new method, a majority of the cell wall p-coumaric acid (55.8-81.5%) was found to be ester-linked to cell wall components, mainly to lignin, and about half of the cell wall ferulic acid is etherified through its phenolic oxygen to the cell wall lignin component, whereas the remainder is esterified to the cell wall hemicelluloses and/or lignin in different plant materials.     

Estimation and decomposition pattern of the lignin component in forest humus layers

Lignin is one of the most abundant polymeric organic constituents of forest litter. Due to its molecular structure and heterogeneity the isolation of lignin in an unchanged form and its exact determination in forest humus have not proved possible. The oxidative degradation with CuO provides a specific method for the characterization of intact lignin structures in forest humus layers. The sum of phenolic CuO oxidation products gives an overall pattern of lignin decomposition. The degree of alteration of the remnant lignin is described by the acid-to-aldehyde ratio (Ac:Al) of syringyl and vanillyl units for angiosperm and gymnosperm lignin and the ratio of syringyl-to-vanillyl units (S:V) for angiosperm lignin.The lignin component of three different forest humus layers investigated was partly decomposed. The residual lignin fraction had undergone extensive modification during microbial decomposition. The chemical changes occurring in the lignin molecule during decomposition in forest humus layers suggest similar mechanisms of lignin degradation (“white-rot”) are shared by wood and forest litter.     

Changes of lignin phenols and neutral sugars in different soil types of a high-elevation forest ecosystem 25 years after forest dieback

Long-term effects of forest disturbance 25 yr ago on lignin and non-cellulosic polysaccharide pools in an unmanaged high-elevation Norway spruce (Picea abies L. [Karst.]) forest were investigated by comparing three dieback sites with three adjacent control sites with non-infested spruce on identical soils. Samples were taken from the forest floor and the mineral soil; one Ah horizon sample per site was physically fractionated into density and particle size fractions. Additionally, changes in the above- and belowground input of lignin and non-cellulosic polysaccharides after forest dieback were quantified. Lignin and its degree of structural alteration in plant and soil samples were assessed by CuO oxidation and subsequent analysis of the lignin phenols. Non-cellulosic polysaccharides were determined after hydrolysis with trifluoroacetic acid (TFA), derivatisation of their neutral sugar monomers by reduction to alditols, and subsequent acetylation. The total plant-derived input of lignin and non-cellulosic polysaccharides to the soil was similar for the dieback and the control sites. The chemical composition of the input has changed considerably after forest dieback, as shown by significantly higher syringyl/vanillyl (S/V) ratios and significantly lower (galactose+mannose)/(arabinose+xylose) (GM/AX) ratios. This indicates a changed plant input and a higher contribution of microbial sugars. Contents of lignin phenols in the forest floor and coarse particle size fractions of the A horizons were significantly smaller at the dieback sites (p<0.01). Moreover, larger acid-to-aldehyde ratios of vanillyl units (Ac/Al)_v indicated an increased degree of lignin phenol alteration. Also contents of neutral sugars were significantly (p<0.01) smaller in the forest floor, but not in the A horizons of the dieback sites. The GM/AX mass ratios as well as the (rhamnose+fucose)/(arabinose+xylose) (RF/AX) ratios in the forest floor and coarse particle size fractions of the mineral topsoil were significantly (p<0.01) larger after forest dieback, indicating a larger relative contribution of microbial sugars. In general, the lignin phenol and neutral sugar pools of all three soil types exhibited similar response patterns to the changed site conditions. Our results demonstrate that the lignin and neutral sugar pools of humic topsoil horizons are highly sensitive to forest disturbances. However, the two compounds show different patterns in the mineral soil, with the major neutral sugar pool being stabilized against changes whereas the lignin phenol pool decreases significantly.     

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.     

Chitosan treatment of wheat seeds induces resistance to Fusarium graminearum and improves seed quality.

Chitosan treatment (2-8 mg/mL) of wheat seeds significantly improved seed germination to recommended seed certification standards (>85%) and vigor at concentrations >4 mg/mL, in two cultivars of spring wheat (Norseman and Max), by controlling seed-borne Fusarium graminearum infection. The germination was <80% in the control and >85% in benomyl- and chitosan-treated seeds. Seed-borne F. graminearum was reduced to >50% at higher chitosan treatments compared to the control. Synthesis of phenolic acids was stimulated in primary leaves following chitosan treatment, and levels of these phenolic acids, especially ferulic acid, increased significantly with increasing chitosan concentration. Lignin content of primary leaves also showed a similar pattern. The synthesis of precursors of lignin such as p-coumaric, ferulic, and sinapic acids and phenolic acids having antimicrobial activity such as benzoic, p-coumaric, caffeic, protocatechuic, chlorogenic, ferulic, and gallic acids was also stimulated by chitosan treatment. The induction of phenolic acids and lignin was significantly lower in cv. Max compared to Norseman. Chitosan also inhibited fungal transmission to the primary roots of germinating seedlings. Results suggest that chitosan controlled seed-borne F. graminearum infection and increased the resistance in seedlings by stimulating the accumulation of phenolics and lignin. Thus, chitosan has a potential for improvement of seed quality and enhancement of crop yields as well as increased value of stored grains for food and feed.     

Structural characterization of the lignin from the nodes and internodes of Arundo donax reed

Milled wood lignin (MWL) and dioxane lignin (DL) from different morphological regions (nodes and internodes) of Arundo donax reed were subjected to a comprehensive structural characterization by (13)C, (1)H NMR, FTIR, and UV spectroscopies and functional analysis. The permanganate and nitrobenzene oxidation methods were also applied to the in situ lignins. Both node and internode lignins are HGS-type lignins, with a significant amount of H units (including p-coumaric acid type structures). The S/G ratio (1.13-1.32), the weight-average molecular weight (20,400-24,500), the methoxyl group content (0.90-0.98), the phenolic hydroxyl group content (0.23-0.27), and the aliphatic hydroxyl group content (1.00-1.09) are not very different in the lignins from nodes and internodes. However, some structural differences between node and internode lignins were observed. The former has much more phenolic acids (p-coumaric and ferulic), 8.8% in node versus 1.2% in internode and less beta-O-4 (0. 32 and 0.49 per aromatic unit in node and internode, respectively). In situ node lignin is more condensed than internode lignin.     

Lignin turnover kinetics in an agricultural soil is monomer specific

Lignin transformation and decomposition products are generally considered a major source of stable soil organic matter (SOM). Nevertheless this process remains poorly understood in part because lignin is a heterogeneous biopolymer composed of several types of phenol monomers, which potentially display specific and contrasting decomposition kinetics in soils. Here, we compared the specific in situ turnover kinetics of individual lignin monomers in a Paris-basin loamy soil through natural ¹³C labeling of SOM generated in a series of 1-9-year chronosequences of maize monoculture (C4, δ¹³C −12‰) replacing wheat (C3, −27‰). Lignin monomers were released by CuO oxidation, quantified by gas chromatography (GC)/flame ionization detection (FID) and their ¹³C content was determined by GC coupled via a combustion interface to isotope ratio mass spectrometry (GC/C-IRMS). We calculated the proportion of C4-derived OC in lignin monomer pools by applying the isotopic mass balance equation to each lignin monomer.Individual C4-derived phenols displayed contrasting accumulation rates in soils over time, confirming the monomer-specific nature of their transformation kinetics. In proportion to total lignin phenols in soils, syringyl (S) and cinnamyl (C) phenols from maize accumulated faster than their vanillyl (V) counterparts. Consequently, the turnover kinetics of lignin-derived V-moieties may be slower than those of S and C ones. Incorporation of maize-derived carbon was faster in the aldehyde than in the acid pool for V-type units, while the opposite was observed for S-units. These in situ trends for phenol monomers and V-, S- and C-moieties were remarkably similar to the trends described in the literature with laboratory incubation or litterbag studies.None of the observed kinetics had a linear shape. Using only the extreme points of the chronosequence to calculate the kinetic parameters would result, for all the lignin monomers, in underestimating the turnover kinetics at the beginning of the kinetics and overestimating it for longer times. This observation underlines the importance of comprehensive ¹³C time-sequence labelling experiments such as provided at the Closeaux site, to accurately compute the kinetic parameters of SOM for the 1st years after the vegetation change.     

Plant lignin and nitrogen contents control carbon dioxide production and nitrogen mineralization in soils incubated with Bt and non-Bt corn residues

Bt (Bacillus thuringiensis) corn is reported to produce lignin-rich residues, compared to non-Bt (NBt) corn, suggesting it is more resistant to decomposition. As the Bt gene is expressed selectively in stem and leaf tissue, it could affect lignin distribution in corn, which naturally has greater lignin content in roots than in stems and leaves. Our objective was to evaluate the effects of corn plant components, the Bt gene and elevated-lignin inputs on decomposition. Roots, stems and leaves from Bt corn and NBt corn isolines enriched with ¹³C and ¹⁵N were finely ground and mixed separately with soil, then incubated at 20 °C for 36 weeks. The effect of elevated lignin on decomposition was tested by adding a commercial lignin source (indulin lignin) to half of the samples. In addition to weekly CO₂ analysis and regular measurement of N mineralization, the degree of lignin degradation was evaluated at 1 and 36 weeks from the acid to aldehyde ratio (Ad/Al) of vanillyl and syringyl lignin-derived phenols. The CO₂ production and N mineralization was lower in root-amended soils than stem- and leaf-amended soils. The Bt genetic modification increased CO₂ production from stem-amended soils (P < 0.05) and decreased N mineralization in root-amended soils. The ¹³C and ¹⁵N results also showed more residue-C and -N retained in soils mixed with NBt stem residues. After 36 weeks leaf- and stem-amended soils with indulin lignin had a lower Ad/Al ratio and were less degraded than soils without exogenous lignin. In conclusion, plant lignin and nitrogen contents were good predictors of CO₂ production and N mineralization potential. Corn roots decomposed more slowly than aboveground components emphasizing the importance of recalcitrant root residues in sustaining the organic matter content of soil.     

Separation,characterization, and quantitation of benzoic and phenolic antioxidants in American cranberry fruit by GC-MS

A GC-MS method is reported for separation and characterization of widely different amounts of benzoic and phenolic acids as their trimethylsilyl derivatives simultaneously in cranberry. Fifteen benzoic and phenolic acids (benzoic, o-hydroxybenzoic, cinnamic, m-hydroxybenzoic, p-hydroxybenzoic, p-hydroxyphenyl acetic, phthalic, 2,3-dihydroxybenzoic, vanillic, o-hydroxycinnamic, 2,4-dihydroxybenzoic, p-coumaric, ferulic, caffeic, and sinapic acid) were identified in cranberry fruit in their free and bound forms on the basis of GC retention times and simultaneously recorded mass spectra. Except for benzoic, p-coumaric, caffeic, ferulic, and sinapic acids, 10 other phenolic acids identified have not been reported in cranberry before. The quantitation of the identified components was based on total ion current (TIC). The experimental results indicated cranberry fruit contains a high content of benzoic and phenolic acids (5.7 g/kg fresh weight) with benzoic acid being the most abundant (4.7 g/kg fresh weight). The next most abundant are p-coumaric (0.25 g/kg fresh weight) and sinapic (0.21 g/kg fresh weight) acid. Benzoic and phenolic acids occur mainly in bound forms and only about 10% occurs as free acid.     

Variability in the release of free and bound hydroxycinnamic acids from diverse malted barley (Hordeum vulgare L.) cultivars during wort production

Volatile phenols have long been recognized as important flavor contributors to the aroma of various alcoholic beverages. The two main flavor-active volatile phenols in beer are 4-vinylguaiacol and 4-vinylphenol. They are the decarboxylation products of the precursors ferulic acid and p-coumaric acid, respectively, which are released during the brewing process, mainly from malt. In this study, the variability in the release of free and ester-bound hydroxycinnamic acids from nine malted barley ( Hordeum vulgare L.) varieties during wort production was investigated. A large variability between different barley malts and their corresponding worts was observed. Differences were also found between free ferulic acid levels from identical malt varieties originating from different malt houses. During mashing, free hydroxycinnamic acids in wort are both water-extracted and enzymatically released by cinnamoyl esterase activity. Esterase activities clearly differ between different barley malt varieties. Multiple linear regression analysis showed that the release of ferulic acid during mashing did not depend only on the barley malt esterase activity but also on the amount of ester-bound ferulic acid initially present in the wort and on its endoxylanase activity. The study demonstrates the importance of selecting a suitable malt variety as the first means of controlling the final volatile phenol levels in beer.     

Characterization of the p-coumaric acid decarboxylase from Lactobacillus plantarum CECT 748(T)

It was previously reported that cell cultures from Lactobacillus plantarum CECT 748 (T) were able to decarboxylate phenolic acids, such as p-coumaric, m-coumaric, caffeic, ferulic, gallic, and protocatechuic acid. The p-coumaric acid decarboxylase (PDC) from this strain has been overexpressed and purified. This PDC differs at its C-terminal end when compared to the previously reported PDC from L. plantarum LPCHL2. Because the C-terminal region of PDC is involved in enzymatic activity, especially in substrate activity, it was decided to biochemically characterize the PDC from L. plantarum CECT 748 (T). Contrarily to L. plantarum LPCHL2 PDC, the recombinant PDC from L. plantarum CECT 748 (T) is a heat-labile enzyme, showing optimal activity at 22 degrees C. This PDC is able to decarboxylate exclusively the hydroxycinnamic acids p-coumaric, caffeic, and ferulic acids. Kinetic analysis showed that the enzyme has a 14-fold higher K(M) value for p-coumaric and caffeic acids than for ferulic acid. PDC catalyzes the formation of the corresponding 4-vinyl derivatives (vinylphenol and vinylguaiacol) from p-coumaric and ferulic acids, respectively, which are valuable food additives that have been approved as flavoring agents. The biochemical characteristics showed by L. plantarum PDC should be taken into account for its potential use in the food-processing industry.     

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.     

Land-use effects on the composition of organic matter in particle-size separates of soil: I. Lignin and carbohydrate signature

Soil from Eutrochrept A horizons under long-term spruce forest (Sf), mixed deciduous forest (Df), permanent grassland (Gp) and arable rotation (Ar) was fractionated according to particle size and analysed for contents of C, N, lignin-derived phenols and carbohydrates. Whole soil from Sf, Df, Gp and Ar contained 84, 59, 73 and 25 g C kg^?1 soil, respectively. For all sites, the C content declined and C/N ratio increased in the order: clay (<2 μm), silt (2–20 μm), sand (20–2000 μm). Clay and silt were significantly lower in C in Ar than in Sf, Df and Gp, C associated with sand being substantially lower under arable rotation. The yield of lignin-derived phenols decreased and carboxyl functionality and methoxyl demethylation of lignin derivatives increased with decreasing particle size, indicating a progressive lignin alteration. Whole soil from Sf and Gp was substantially higher in vanillyl (V), syringyl (S) and cinnamyl (C) units (VSC) than soil from Df and Ar. Compared to whole soil, clay was depleted and sand enriched in VSC. Only sand appeared to be affected significantly by land use. Sand from Ar and Df was more enriched in VSC than sand from Gp and Sf. Whole soil carbohydrates decreased in the order: Gp>Ar>Df>Sf. Sand- and clay-sized separates were enriched in carbohydrates compared to silt. Carbohydrates in sand were mainly of plant origin whereas microbially-derived sugars accounted for a larger proportion in the clay. Compared to Sf, Df and Gp, clay from Ar was enriched and sand depleted in microbial sugars. Lignin and carbohydrate distribution patterns indicate that organic matter was in a more advanced stage of decomposition in the sand separates from forest than from agricultural A horizons. The forest soils also show a higher degree of oxidative changes in lignin associated with clay. In contrast, differences between silt from the four A horizons were small.     

Effect of phenolic structures on the degradability of cell walls isolated from newly extended apical internode of tall fescue (Festuca arundinacea Schreb.)

Apical internodes of tall fescue (Festuca arundinacea Schreb. var. Clarine) harvested at flowering were sectioned into 5 or 10 equal parts to study in situ degradability and cell wall composition, respectively. The basal (youngest) section had the greatest primary wall content. Cell walls in the upper (older) sections had the highest xylose/arabinose ratio and lignin content and a lignin rich in syringyl units, all typical of extensive secondary wall development. Almost all of the p-coumaric (p-CA) and about half of the ferulic acid (FA) were released by 1 M NaOH and presumed to be ester-linked. The total FA content was approximately double that of p-CA in all sections other than the youngest with a distribution similar to that of total p-CA. However, the ratio of esterified to ether and ether plus ester linked (Et & Et+Es) FA differed with age. Whereas the esterified form remained essentially constant ( approximately 4.5 g/kg of cell wall), Et & Et+Es ferulate increased with increasing age of the tissue and was significantly related to lignin deposition (r = 0.79, P < 0.01). The extent of cell wall degradation after 48 h of incubation in the rumen was inversely related to maturity, falling from 835 g/kg of dry matter in the youngest section to 396 g/kg in the oldest. Both the rate and extent of cell wall degradation were significantly negatively related to the ratio of xylose to arabinose, lignin content, proportion of syringyl units present in lignin, and concentration of Et & Et+Es FA present. A positive relationship between Et & Et+Es FA was also found, with the rate (P < 0.01) being better correlated than the extent (P < 0.05) of cell wall degradation. Application of the newly extended internode model to fescue produced results consistent with the view that both the lignin content and the extent to which lignin was covalently bound to the other wall polymers crucially influenced the rate and extent of degradation.     

Impact of plant cell wall network on biodegradation in soil: Role of lignin composition and phenolic acids in roots from 16 maize genotypes

Residue quality is a key factor governing biodegradation and the fate of C in soil. Most investigations of relationships existing between crop residue quality and soil decomposition have been based on determining the relative proportions of soluble, cellulose, hemicellulose and lignin components. However, cell wall cohesion is increased by tight interconnections between polysaccharides and lignin that involve cross-linking agents (phenolic acids). The aim of this study was to determine the role of lignin composition and phenolic acids on short- to medium-term decomposition of maize roots in soil. Sixteen maize genotypes, presenting a range of chemical characteristics related to root lignin and phenolic acids, were used. The main components were characterized by Van Soest (VS) extraction and cell wall acid hydrolysis, and the non-condensed Syringyl and Guaicyl lignin monomers, esterified phenolic acids and etherified phenolic acids were determined. Maize roots were then incubated in soil under controlled conditions (15 °C, −80 kPa moisture) for 796 days. Results showed that VS extraction over-estimated the structural hemicellulose content and that VS lignin was more recalcitrant than Klason lignin. The tremendous effect of cell wall chemical characteristics was shown by marked variations (almost two-fold differences in C mineralization), between the 16 maize roots. Decomposition was controlled by soluble residue components in the short term whereas lignin and the interconnections between cell wall polymers were important in the long-term. Notably the cell wall domain rich in non-condensed lignin and esterified phenolic acids was prone to decomposition whereas the presence of etherified ferulic acids seemed to hamper cell wall decomposition.     

Degradation of hemicellulose, cellulose and lignin in decomposing spruce needle litter in relation to N

Decomposing needles from a Norway spruce forest in southern Sweden were studied for 559 days under laboratory conditions. Falling needles were collected in control (Co) plots and plots that had received 100 kg N ha⁻¹ yr⁻¹ as (NH₄)₂SO₄ for 9 years under field conditions. One of the aims was to determine whether the previously documented low decomposition rate of the N fertilized (NS) needles could be explained by a lower degradation degree of lignin. The lignin content was studied using the alkaline CuO oxidation method, the Klason lignin method and CPMAS ¹³C NMR spectroscopy. The amounts of cellulose and hemicellulose were also determined.The fertilized needle litters initially decomposed faster than the unfertilized, but later this reaction reversed, so that at the end the mass loss was 45% initial C in the control and 35% initial C in NS. Klason lignin decreased with time in both treatments and overall, the change of Klason lignin mirrored the litter mass loss. No major difference as regards the decomposition of hemicellulose occurred between the treatments, whereas significantly lower concentrations of cellulose were found in NS needles throughout the incubation. The CuO derived compounds (VSC) were somewhat lower in NS needles throughout the decomposition time. Initially, VSC increased slightly in both treatments, which contradicts the Klason lignin data. There was a weak positive relationship (p>0.05) between VSC and Klason lignin. Both vanillyls compounds (V) and cinnamyl compounds (Ci) increased slightly during decomposition, whereas syringyl compounds (S) vanished entirely. The lignin degradation degree, i.e. the acid-to-aldehyde ratio of the vanillyl compounds expressed as (Ac/Al)_v, showed no significant effect of treatment. The ¹³C NMR analyses of the combined samples showed increased content of aromatic C with increasing decomposition time. The carbohydrate content (O-alkyl C) was lower in the fertilized needle litter throughout the incubation time. The alkyl C content tended to increase with decomposition time and N fertilization. The alkyl C/O-alkyl C ratios increased in both treatments during the incubation. The NMR results were not tested statistically.In conclusion, no major difference concerning lignin degradation could be found between the unfertilized and N fertilized needle litter. Thus, the study contradicts the hypothesis that higher amounts of N reduce lignin degradation. The reduced biological activity is probably due to direct N effects on the microorganisms and their decomposing ability.