Processes controlling the production of aromatic water-soluble organic matter during litter decomposition

Dissolved organic matter (DOM) plays a fundamental role for many soil processes. For instance, production, transport, and retention of DOM control properties and long-term storage of organic matter in mineral soils. Production of water-soluble compounds during the decomposition of plant litter is a major process providing DOM in soils. Herein, we examine processes causing the commonly observed increase in contribution of aromatic compounds to WSOM during litter decomposition, and unravel the relationship between lignin degradation and the production of aromatic WSOM. We analysed amounts and composition of water-soluble organic matter (WSOM) produced during 27 months of decomposition of leaves and needles (ash, beech, maple, spruce, pine). The contribution of aromatic compounds to WSOM, as indicated by the specific UV absorbance of WSOM, remained constant or increased during decomposition. However, the contribution of lignin-derived compounds to the total phenolic products of ¹³C-labelled tetramethylammonium hydroxide (¹³C-TMAH) thermochemolysis increased strongly (by >114%) within 27 months of decomposition. Simultaneous changes in contents of lignin phenols in solid litter residues (cupric oxide method as well as ¹³C-TMAH thermochemolysis) were comparably small (−39% to +21% within 27 months). This suggests that the increasing contribution of lignin-derived compounds to WSOM during decomposition does not reflect compositional changes of solid litter residues, but rather the course of decomposition processes. In the light of recently published findings, these processes include: (i) progressive oxidative alteration of lignin that results in increasing solubility of lignin, (ii) preferential degradation of soluble, non-lignin compounds that limits their contribution to WSOM during later phases of decomposition.     

Amounts and degradability of dissolved organic carbon from foliar litter at different decomposition stages

Litter is one of the main sources of dissolved organic carbon (DOC) in forest soils and litter decomposition is an important control of carbon storage and DOC dynamics. The aim of our study was to evaluate (i) effects of tree species on DOC production and (ii) relationships between litter decomposition and the amount and quality of DOC. Five different types of leaves and needles were exposed in litterbags at two neighboring forest sites. Within 12 months we sampled the litterbags five times and leached aliquots of field moist litter in the laboratory. In the collected litter percolates we measured DOC concentrations and recorded UV and fluorescence spectra in order to estimate the aromaticity and complexity of the organic molecules. Furthermore, we investigated the biodegradability of DOC from fresh and decomposed litter during 6 weeks incubations. Fresh sycamore maple litter released the largest amounts of DOC reaching about 6.2% of litter C after applying precipitation of 94 mm. We leached 3.9, 1.6, 1.0 and 3.3% carbon from fresh mountain ash, beech, spruce and pine litter, respectively. In the initial phase of litter decomposition significantly decreasing DOC amounts were released with increasing litter mass loss. However, after mass loss exceeds 20% DOC production from needle litter tended to increase. UV and fluorescence spectra of percolates from pine and spruce litter indicated an increasing degree of aromaticity and complexity with increasing mass loss as often described for decomposing litter. However, for deciduous litter the relationship was less obvious. We assume that during litter decomposition the source of produced DOC in coniferous litter tended toward a larger contribution from lignin-derived compounds. Biodegradability of DOC from fresh litter was very high, ranging from 30 to 95% mineralized C. DOC from degraded litter was on average 34% less mineralizable than DOC from fresh litter. Taking into account the large DOC production from decomposed needles we can assume there is an important role for DOC in the accumulation of organic matter in soils during litter decomposition particularly in coniferous forests.     

Decomposition of beech leaves (Fagus sylvatica) and spruce needles (Picea abies) in pure and mixed stands of beech and spruce

The decomposition of spruce needles and beech leaves was investigated in a 30- and 120-yr-old beech, spruce and mixed (beech/spruce) forest using 1 mm mesh litterbags. The mass loss, content of C, N and water and microbial biomass, basal respiration and specific respiration of the litter materials were analyzed after exposure for 1.5, 3, 6, 9, 12, 18 and 24 months in the field. Decomposition of both types of litter was faster in beech than in spruce stands and after 24 months loss of C from litter materials was at a maximum in beech stands (>60%) and considerably less in the spruce and mixed stands (ca. 40%). Generally, spruce needles decomposed more rapidly than beech leaves, but the faster decay was not associated with higher N concentrations. Rather, N was accumulated more rapidly in beech leaves. Concomitantly, in beech stands microbial biomass of beech leaves exceeded that of spruce needles indicating that beech leaves consist of more favorable resources for microorganisms than spruce needles. Differences in decomposition between beech leaves and spruce needles were most pronounced in beech stands, intermediate in mixed stands and least pronounced in spruce stands. Decomposition, N content and microbial biomass in litter materials exposed in the 120-yr-old stand consistently exceeded that in the 30-yr-old stand indicating adverse conditions for litter decay in regrowing stands. Generally, mixed stands ranked intermediate between spruce and beech monocultures for most of the variables measured indicating that the adverse conditions for litter decay and microorganisms in spruce forest are effectively counteracted by admixture of beech to spruce monocultures. It is concluded that the accumulation of litter materials in spruce forests is not due to the recalcitrance of spruce needles to decay. Rather, adverse environmental conditions such as high polyphenol contents in the litter layer of spruce stands retard decomposition processes; spruce needles appear to be more sensitive to this retardation than beech leaves.     

Effects of tree species and topography on soil chemistry, litter quality, and decomposition in Northeast Turkey

Leaf litters from beech (Fagus orientalis Lipsky.) and oak (Quercus robur L.), and needle litters from fir (Abies nordmanniana Spach.) and pine (Pinus sylvestris L.) trees were collected from north-facing site and south-facing site and at three slope positions (top, middle and bottom) on each aspect that varied in soil chemical characteristics (soil pH, cation exchange capacity and base saturation). The litters were analysed for initial total carbon, nitrogen, acid detergent fibre, lignin and cellulose concentrations. Nitrogen, acid detergent fibre and lignin concentrations and carbon:nitrogen and lignin:nitrogen ratios varied significantly within and between species according to soil chemical characteristics on aspects and slope positions. Litter decomposition was studied in the field using the litterbag technique. The litters were placed on two aspects and at three slopes on each aspect in October 2001, and were sampled every 6-month for 2 years. The main effects of aspect, species and slope position on decomposition rates were all statistically significant. Oak leaf litter showed highest decomposition rates, followed by pine, fir and beech litter, and the litters placed on north-facing site decomposed faster than those on the south-facing site. The litters placed at the top slope position decomposed slower than at those at either the bottom or middle positions. Initial lignin concentrations explained most of the variation in decomposition rates between species, and within species for the aspects and the slope positions, but the explained variance showed differences between aspects and slope positions. This result illustrates the important point that litter quality may define the potential rates of microbial decomposition but these are significantly influenced by the biotic and abiotic environment in which decomposition takes place.     

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.     

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.     

Characterization of dissolved organic matter in decomposing Norway spruce and silver birch litter

Dissolved organic matter (DOM) plays an important role in transport, storage and cycling of carbon (C) and nitrogen (N) in forest soils where litter is one of the main sources. The aim was to study the amount and characteristics of DOM leached from freshly fallen litters of silver birch (Betula pendula Roth.), Norway spruce (Picea abies (L.) Karst.) and their mixture during decomposition. DOM was collected after irrigation on eight occasions during 252 days incubation in the laboratory at about 18°C, including one freeze‐thaw cycle. During the incubation about 33–35% of C from birch and spruce litter and 40% of C from their mixture was lost. The total cumulative flux of dissolved organic carbon (DOC) from the mixture of litters was approximately 40% larger than that from single litters. The flux of DOC, DON, phenolic compounds and proteins followed a two‐stage pattern during decomposition. In the first stage the initially large fluxes decreased gradually. In the second stage, after freezing and thawing, the fluxes tended to increase again. Mixing birch and spruce litters and a freeze‐thaw cycle seems to increase the decomposition of litter and result in the increased flux of DOC, DON and phenolic compounds. The flux of hemicelluloses and the degradability of DOM were large at the first leaching occasion and decreased during the incubation. Birch had a 40% larger total flux of easily degradable DOM than spruce, supporting the previous consistent signs of greater microbial biomass and activities related to C and N cycling in soil under birch than under spruce. It is known that recalcitrant DOM might be stabilized whereas labile DOM may promote microbial activity and nutrient cycling. We conclude that the storage and cycling of C and N is affected by both tree species and degradation stage of litter in forest soils.     

Veränderungen in der stofflichen Zusammensetzung von Buchenstreu und Gerstenstroh beim Abbau unter Laborbedingungen

Chemical changes of beech litter and barley straw during decomposition under laboratory conditions Beech litter and barley straw were incubated at 20°C and 70% of maximum water holding capacity in the presence and absence of artificial “soil” and earthworms (Eisenia fetida). Results show that beech litter biodegradation was enhanced by E. fetida during the first part, but delayed in later stages of the incubation period, as indicated by the changes of ash contents and C-to-N ratios with progressive decomposition. In the long run the organic matter (OM) of beech litter tended to be stabilised through the action of worms. In contrast, for barley straw a more intense biodegradation was observed in the presence of E. fetida throughout the experiment. Almost 80% of litter and straw OM could be identified by means of wet chemical degradation methods (70% polysaccharides, lignin; 10% lipids, protein). The proportion of the exclusively plant-derived constituents cellulose and lignin showed a partly strong decrease with progressive decomposition; simultaneously the contents of also microbially synthesised components such as non-cellulosic polysaccharides and protein increased. Changes of the non-cellulosic polysaccharide-cellulose-quotients (NCQ), lignin-cellulose-quotients (LCQ), and acid-to-aldehyde ratios (ac/al)_v and (ac/al)_s in the residual lignin reflected well the litter decomposition process. At the end of the experiment - irrespective of treatments - the degree of beech litter biodegradation was comparable to that of Of-Oh transitional layers in beech-derived forest humus profiles. In the case of barley straw only NCQ and LCQ, but not (ac/al)_v,s were valuable parameters for the characterisation of the decomposition process.     

Interactions between litter quality, decomposition and soil fertility: a laboratory study

Leaf litters from beech (Fagus sylvatica L.) and oak (Quercus robur L.) trees were collected from mixed, deciduous woodlands growing on three soil types that varied in mineral nutrient concentrations and N mineralisation potential. Litter quality, including %N, %Mn, %P, acid detergent fibre, cellulose, Klason lignin, phenylpropanoid constituents of lignin, hexose and pentose sugar (mainly from hemicelluloses) varied within species according to soil type. However, oak and beech showed the opposite responses to soil nutrient status for most of these variables. The litters were incubated in the laboratory for 12 months (at 18 °C and constant moisture) on beds of forest floor material from two soils of contrasting high nutrient material (HNM) or low nutrient material (LNM) nutrient status to investigate litter quality and substrate interactions. At 4, 8 and 12 months there were significant differences in mass losses from oak and beech litters from all sites, and for each litter type exposed to the HNM and LMN soils. At 12 months mean mass losses were higher for HNM treatment (38.7% oak, 27.8% beech) than for the LNM treatment (30.6% oak, 25.5% beech). However, the beech and oak litters from the different sites consistently responded in opposite ways on the same soil treatment reflecting site-related effects on litter quality. Initial concentration of Klason lignin was the best predictor for mass losses from litter species and litter types. Intra-specific variation in rates of litter decomposition of beech and oak litters from different sites, and differences in their interactions with the two forest floor materials, illustrate the complexities of proximate controls on decomposition that are often masked in system-level studies.     

Decomposition of sun and shade leaves from three deciduous tree species,as affected by their chemical composition

Freshly fallen leaf litter from sweet chestnut (Castanea sativa Mill), oak (Quercus robur L.) and beech (Fagus sylvatica L.) trees were classified into sun, intermediate and shade leaf types and analysed for N, acid detergent fibre, holocellulose, and lignin. In addition, the sugar constituents of structural polysaccharides (mainly from hemicelluloses) were determined after trifluoracetic acid (TFA) hydrolysis, and the phenylpropanoid (PPD) derivatives of lignin after alkaline CuO oxidation. The litters were decomposed in laboratory microcosms for 2 years. Decomposition rates were initially rapid and then plateaued, but differences in mass losses for the leaf litter categories, and between the three species, were significant at 6, 12, 18 and 24 months. Mean mass losses after 24 months were 49.6% for chestnut, 40.4% for oak and 26.3% for beech. Mean losses for chestnut, oak and beech litter categories were 48.6%, 38.2% and 24.6%, respectively, for sun leaves, and 51.0%, 44.5% and 28.5%, respectively, for shade leaves. Initial lignin concentrations showed a negative correlation with mass losses over the first 6 months but initial acid detergent fibre was a better predictor of decomposition rates after 24 months. Within species, however, total extractable sugars and PPD concentrations reflected differences in decomposition rates between the different categories of leaf types. The analysis for specific carbohydrates and lignin derivatives improved the resolution of litter quality characterisation but did not explain the observed patterns of decomposition in long-term laboratory incubations. It is suggested that these may be affected by influence of the culture conditions on the composition of fungal communities.     

Partitioning of carbon and nitrogen during decomposition of 13C15N‐labeled beech and ash leaf litter

The aim of this study was to determine the influence of leaf‐litter type (i.e., European beech—Fagus sylvatica L. and European ash—Fraxinus excelsior L.) and leaf‐litter mixture on the partitioning of leaf‐litter C and N between the O horizon, the topsoil, the soil microbial biomass, and the CO₂ emission during decomposition. In a mature beech stand of Hainich National Park, Thuringia, Germany, undisturbed soil cores (?? 24 cm) were transferred to plastic cylinders and the original leaf litter was either replaced by ¹³C¹⁵N‐labeled beech or ash leaf litter, or leaf‐litter‐mixture treatments in which only one of the two leaf‐litter types was labeled. Leaf‐litter‐derived CO₂‐C flux was measured every second week over a period of one year. Partitioning of leaf‐litter C and N to the soil and microbial biomass was measured 5 and 10 months after the start of the experiment. Ash leaf litter decomposed faster than beech leaf litter. The decomposition rate was negatively related to initial leaf‐litter lignin and positively to initial Ca concentrations. The mixture of both leaf‐litter types led to enhanced decomposition of ash leaf litter. However, it did not affect beech leaf‐litter decomposition. After 5 and 10 months of in situ incubation, recoveries of leaf‐litter‐derived C and N in the O horizon (7%–20% and 9%–35%, respectively) were higher than in the mineral soil (1%–5% and 3%–8%, respectively) showing no leaf‐litter‐type or leaf‐litter‐mixture effect. Partitioning of leaf‐litter‐derived C and N to microbial biomass in the upper mineral soil (< 1% of total leaf‐litter C and 2%–3% of total leaf‐litter N) did not differ between beech and ash. The results show that short‐term partitioning of leaf‐litter C and N to the soil after 10 months was similar for ash and beech leaf litter under standardized field conditions, even though mineralization was faster for ash leaf litter than for beech leaf litter.     

Effects of fungal inocula on the decomposition of lignin and structural polysaccharides in Pinus sylvestris litter

 Litter bags containing sterile Scots pine (Pinus sylvestris) needles (19.8% lignin, 26.5% cellulose and 0.34% N) were inoculated with two species of fungi in the laboratory and then placed in the litter layer of a pine plantation. Marasmius androsaceus, which can degrade lignocellulose, was initially displaced by other fungal colonisers and was not detected in the litter after 2–3 months; but was re-isolated from the needles after 12 months. Trichoderma viride, which is a cellulolytic species and also antagonistic to other fungi, dominated the litter throughout the experiment. The control litter was naturally colonised by litter fungi. After 12 months, mass losses were similar at 52% for M. androsaceus and 48% for T. viride, compared with 36% for the control litter colonised by a more complex fungal community. Lignin concentrations increased with time in control litter and with T. viride because mass losses of carbohydrates were greater than those of lignin. Litter inoculated with M. androsaceus showed significant lignin decomposition throughout the experiment but cellulose concentrations showed a proportional increase in the first 6 months, suggesting that the fungus was preferentially exploiting hemicellulose and non-structural carbohydrates. Analysis of TFA-extractable sugars (mainly from hemicellulose) and CuO-derived phenylpropanoid moieties from lignin confirmed the differential patterns of resource decomposition which were not evident from total mass losses. During the initial stages of decomposition, T. viride was as effective in utilising structural polysaccharides as the complex fungal community in the control litter. Furthermore, M. androsaceus not only exhibited unexpectedly low cellulolytic activity but also facilitated lignin depolymerisation after the fungus was no longer detectable in the litter. The pre-inoculation of litter with these two fungal species therefore affected the overall dynamics of decomposition at a biochemical level. This study illustrates the importance of understanding the effects and interactions of specific fungi, rather than assumptions about the functional competence of diverse communities, on the processes of litter decomposition. Received: 5 July 2000     

Home-field advantage of litter decomposition and nitrogen release in forest ecosystems

Litter decomposition is a major fundamental ecological process that regulates nutrient cycling, thereby affecting net ecosystem carbon (C) storage as well as primary productivity in forest ecosystems. Litter decomposes in its home environment faster than in any other environment. However, evidence for this phenomenon, which is called the home-field advantage (HFA), has not been universal. We provide the first HFA quantification of litter decomposition and nutrient release through meta-analysis of published data in global forest ecosystems. Litter mass loss was 4.2 % faster on average, whereas nitrogen (N) release was 1.7 % lower at the home environment than in another environment. However, no HFA of phosphorus (P) release was observed. Broadleaf litter (4.4 %) had a higher litter mass loss HFA than coniferous litter (1.0 %). The positive HFA of N release was found in the coniferous litter. Mass loss HFA was significantly and negatively correlated with the initial lignin:N litter ratio. The litter decomposition and N release HFAs were obtained when mesh size ranged from 0.15 mm to 2.0 mm. The HFA of litter decomposition increased with decomposition duration during the early decomposition stage. The HFA of N release was well correlated with mass loss, and the greatest HFA was at mass loss less than 20 %. Our results suggest that the litter decomposition and N release HFAs are widespread in forest ecosystems. Furthermore, soil mesofauna is significantly involved in the HFA of litter decomposition.     

Changes in chemical composition of Pinus sylvestris needle litter during decomposition along a European coniferous forest climatic transect

The objective of this investigation was to assess the changes in chemical composition (lignin, cellulose, hemicelluloses, non-structural compounds, N, and ash) of decomposing litter. Standard Pinus sylvestris needle litter, originating from southern Sweden, was incubated in litterbags at 15 sites selected from the Netherlands to south Spain. The changes in chemical composition of this litter were determined using near infrared reflectance spectroscopy. The hypothesis was that standard (chemically uniform) litter decomposing under a range of climates would show different dynamics of accumulation and loss of C-fractions, N, and ash, relative to mass loss. It was shown that, for a given mass-loss value (10, 20, 30, 40, or 50%), the proportion of lignin, cellulose, hemicelluloses, non-structural compounds, N, and ash in the decomposing pine needles differed between sites. Lignin concentration in the litter residue at 50% mass loss ranged from approximately 26 to 43%, cellulose from 19 to 27%, hemicelluloses from 7 to 11%, non-structural compounds from 19 to 25%, N from 0.7 to 1.3%, and ash content from 1.4 to 10.1%. Lignin concentrations showed the highest range of variation. Lignin concentrations during decomposition were positively related to moisture factors as significant correlations were found with actual evapotranspiration and were improved in multiple regressions by the mean annual precipitation or the water surplus. Cellulose was degraded further at sites with high precipitation whereas hemicellulose degradation was related to temperature. This leads to the conclusion that the remaining organic matter produced by standard litter decomposition within the studied climatic range of variations tended to be more recalcitrant under wet and warm climatic conditions than under cold or dry climate.     

Lipid fraction in forest litter: Early stages of decomposition

The lipid fractions of leaf or needle litters of ash, beech, birch, larch, oak, pine and spruce generally disappear more rapidly than non-lipid fractions, though the trend may be obscured by extensive fungal colonization as observed in 3-month old oak and ash samples. While the behaviour of most lipid subfractions is approximately species-independent, changes in concentration of material soluble in hot heptane but only sparingly soluble in cold ether are inversely related to bulk disappearance rate. The exceptional behaviour of this fraction in birch litter is perhaps a result of grazing by soil animals being the dominant removal process for birch leaves. Hot acid hydrolysis, presumably of ester linkages to lignin or polysaccharide, liberates a bound lipid fraction composed principally of fatty acids and accounting for up to 32% (in larch) of total lipid. Data for all species reveal rapid liberation and subsequent disappearance of free fatty acids by biochemical processes in the field.     

Decomposition of black locust and black pine leaf litter in two coeval forest stands on Mount Vesuvius and dynamics of organic components assessed through proximate analysis and NMR spectroscopy

Litter quality is an important determinant of soil organic matter formation. Changes of organic components were investigated along decomposition of black locust (Robinia pseudoacacia L.) leaf litter and black pine (Pinus nigra Arn.) needle litter in the native adjacent coeval forest stands. To this purpose, data from proximate analyses were compared with those from CPMAS ¹³C NMR. Newly shed leaf litter of black locust had significantly higher concentrations of ADSS (acid detergent soluble substances) as well as lower concentrations of cellulose and AUR (acid unhydrolyzable residues that include lignin) and higher AUR-to-Cellulose ratio than that of black pine. The ¹³C CPMAS NMR spectra of newly shed leaf litter of black locust and black pine revealed that O-Alkyl-C components (including cellulose and hemicelluloses) accounted, respectively, for 53.8% and 61.4% of the total area of the spectra. All other C fractions were relatively more abundant in black locust than in black pine. Within individual sampling periods, relationships between residual litter mass and concentrations of ADSS, cellulose and AUR were examined, as were relationships between residual litter C and NMR fractions. Four periods were defined based on the slopes of the decomposition curve, with the length of period I defined by the start of a net decrease of AUR. Proximate analyses and NMR data showed changes in chemical composition over the decomposition process, as well as changes in decay rates of the residues, following different paths in the two litters. ADSS decayed faster in black locust litter; in contrast cellulose and AUR decayed faster in that of black pine. AUR concentration increased in both litters during decomposition; however, compared to black pine, the remaining litter of black locust was richer in AUR, despite the lower initial concentration, and had a higher AUR-to-Cellulose ratio. Phenol-C and Aryl-C decayed faster in black locust litter, while Alkyl-C decayed faster in that of black pine. In both litters, mass loss in periods was negatively correlated to concentration of AUR at the start of the periods. C loss in periods was negatively correlated to the concentration at the start of the periods of MC-to-PC (an index of lignin content) in black locust litter and positively correlated to Alkyl-C and O-Alkyl-C in that of black pine. Phenol-C, O-Alkyl-C and Aryl-C were the most decomposable C fractions in black locust. O-Alkyl-C and Alkyl-C were the most decomposable C fractions in black pine. Limit value was lower in black pine than in black locust. Consequently the different pattern of litter decomposition can affect the size of C sequestration in the forest floor and the quality of accumulated organic carbon.     

Adsorption of cellulase components by leaf litter

The competitive adsorption of Trichoderma viride cellulase components to leaf litter was investigated to further elucidate the role of extracellular enzymes as mediators of decomposition processes. Litter analogs were prepared by acid-detergent digestion of senescent Pinus strobus (white pine), Quercus prinus (chestnut oak) and Cornus florida (flowering dogwood) leaves. Enzymatic cellulose digestion was used to produce litter analogs of higher lignin content. The white pine litter analogs had a high affinity for exocellulase and β-glucosidase. Chestnut oak litter preferentially bound endocellulase components and flowering dogwood litter displayed intermediate trends. Natural mixed-deciduous and white pine litters and humus had less capacity for immobilizing cellulase components. The adsorption data are consistent with available information on the binding of cellulase components to purified cellulose and with information on the cellulase activity patterns of decomposing leaf litter.     

CPMAS 13C NMR and IR spectra of spruce and pine litter and of the Klason lignin fraction at different stages of decomposition

Fresh and decomposed spruce and pine litter and the Klason lignin fraction of spruce needles at different stages of decomposition were studied by CPMAS ¹³C NMR and IR spectroscopy as well as by chemical methods. It was shown that decomposition of needles is accompanied by an increase in aliphatic substances and carboxyl group content; the amount of polysaccharides is reduced. It is assumed that stable aliphatic compounds like cutin and lipids of microbial origin will accumulate during litter decomposition and humification. Aromaticity is low and does not alter drastically. The NMR spectra of the Klason lignin fraction show pronounced peaks at 30, 55, 115, 130, 150 and 175 ppm. Obviously, this fraction contains appreciable amounts of aliphatic and carboxyl carbon besides the typical aromatic units of lignin. During decomposition aromaticity decreases whereas the relative amounts of aliphatic substances and carboxyl groups increase. This is probably due to splitting of aromatic ring structures and side chains. The findings agree with the results from chemical analyses.     

Analytical pyrolysis of a soil profile under Scots pine

The chemical properties of pine needle litter cause slow decomposition, which results in an accumulation of highly lignocellulosic material on the forest floor. Decomposition of organic matter is important for the nutrient turnover in pine forests on nutrient-poor soils. We studied the biodegradation of needles in an organic layer focusing on the various stages of lignin degradation by fungi. Samples were obtained from pine needle litter and a stratified organic layer over nutrient-poor sand under a 60-year-old Scots pine (Pinus sylvestris forest stand. Pyrolysis mass spectrometry (PyMS) and pyrolysis gas chromatography mass spectrometry (PyGCMS) were used to characterize the chemical composition of the needles and the soil. The pyrolysis data show that diterpenoid acids are a main component in fresh needles, but rapidly decrease in the organic layer of the soil, as a result of decomposition. The chemical composition of the soil profile is dominated by guaiacyl lignin and polysaccharides from needle litter. The hexose/pentose ratio increases with depth in the soil profile. The partial preservation of hexose polymers is the result of the preferential decomposition of pentose polymers by white-rot fungi, and points to the input of microbially synthesized polysaccharides. Indications for the degradation of guaiacyl lignin are also found in the soil profile. Oxidative reactions by soil fungi result in a shortening of the side chain of the guaiacyl lignin derivatives and an increase of carbonyl and carboxyl groups. These degradational patterns of lignin in the soil profile under Scots pine are similar to those observed in lignin model compounds and wood lignin degraded by fungi under controlled laboratory conditions.     

Leaf decomposition in two semi-evergreen tropical forests: influence of litter quality

Decomposition processes in tropical semi-evergreen forests are still poorly understood. The influence of soil properties and litter quality on decomposition rate was studied in two semi-evergreen forests of Guadeloupe, a forest plantation and a secondary forest, located on different soils. Leaf litter of four tree species was enclosed in litterbags for a 14-month period. Non-linear correlations were calculated between mass loss and the concentration of major leaf components (soluble C, N, lignin, cellulose, tannins, total soluble phenols) in order to determine the best predictor of leaf litter decomposition. Soil physico-chemical properties and ratios between some of the above-mentioned litter quality parameters were also examined as mass loss predictors. In addition, non-linear correlations were calculated between mass loss and litter quality parameters, at successive periods. Litter quality was the main determinant of litter decomposition in the studied forests. Several litter quality parameters were correlated with leaf disappearance, varying according to stages of decomposition. Between 1 month and 2.5 months, the mass loss was correlated negatively with the initial phenol content and with initial lignin:N and (lignin+phenol):N ratios. From 2.5 to 5.5 months, the mass loss was correlated negatively with the initial phenol content and positively with the initial cellulose content. At later stages of decomposition (9-14 months), the mass loss was correlated negatively with the initial tannin content. Differences in soil characteristics and fauna did not seem to be enough to affect decomposition.