Molecular level analysis of long term vegetative shifts and relationships to soil organic matter composition

Soil organic matter (SOM) is one of the earth’s largest reservoirs of actively cycled carbon and plays a critical role in various ecosystem functions. In this study, mineral soils with the same parent material and of similar approximate age were sampled from the same climatic region in Halsey, Nebraska to determine the relationship between overlying vegetation inputs to SOM composition using complementary molecular level methods (biomarker analyses and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy). Soil samples were collected from a native prairie and cedar and pine sites planted on the native prairie. Free and bound lipids isolated from the pine soil were more enriched in aliphatic and cutin-derived compounds than the other two soils. Cinnamyl type lignin-derived phenols were more abundant in the grassland soil than in the pine and cedar soils. Acid to aldehyde ratios (Ad/Al) for vanillyl and syringyl type phenols were higher for the pine soil indicating a more advanced stage of lignin oxidation (also observed by ¹³C NMR) in the soil that has also been reported to have accelerated carbon loss. In agreement with the more abundant aliphatic lipids and cutin-derived compounds, solid state ¹³C NMR results also indicated that the SOM of the pine soil may have received more aliphatic carbon inputs or may have lost other components during enhanced decomposition. The observed relationship between vegetation and SOM composition may have important implications for global carbon cycling as some structures (e.g. aliphatics) are hypothesized to be more recalcitrant compared to others and their accumulation in soils may enhance below ground carbon storage.     

Effect of N content and soil texture on the decomposition of organic matter in forest soils as revealed by solid-state CPMAS NMR spectroscopy

N has a controlling effect on litter biodegradation in the forest floor, while stabilization of organic matter in the mineral soil may be influenced by physical parameters related to soil texture. In this study, in order to understand the processes involved in soil organic matter (SOM) formation, the chemical composition of SOM was followed and evaluated with regards to N contents and soil texture. Samples were taken on sites covered with Norway spruce and displaying contrasting values of C/N ratios in the forest floor. The chemical structure of OM was characterized using solid-state CPMAS ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy, along with Proton Spin Relaxation Editing (PSRE) sequences. Four groups of sampling sites were defined based on the NMR spectra of Oh and A horizons. In each group displaying similar NMR characteristics, N content and soil texture could be highly different among sites. Some Oh horizons with similar NMR spectra had very different N contents. Highly humified OM in Oh horizons were observed mainly on sites with low N contents. Some A horizons with different soil texture displayed similar OM chemical structure. High contents of O-alkyl C in some A horizons could originate from higher fresh root material input.     

Characterization and quantification of biomarkers from biomass burning at a recent wildfire site in Northern Alberta,Canada

The composition of organic matter (OM) in pine vegetation and soil samples from a pine forest which was charred by a wildfire was analyzed using solid-state nuclear magnetic resonance (¹³C NMR) and gas chromatography–mass spectrometry (GC–MS) of solvent extracts to study the effects of thermal alteration on soil organic matter (SOM). The NMR data revealed the presence of unaltered biomolecules (cellulose, proteins) and low contents of aromatic C (15%) in the charred pine wood and cones while the charred soil samples exhibited higher contents of aromatic C (39–56%). The solvent extraction of charred and uncharred plant and soil samples yielded diterpenoids, triterpenoids, steroids, a series of aliphatic lipids, phenols and carbohydrates indicating the predominant input of higher plant OM and minor contributions from microorganisms and/or fauna. The lower yield of solvent extractable aliphatic lipids in the charred samples versus the uncharred samples suggests that these compounds are thermally degraded during a wildfire. Molecular markers for the burning of cellulose (levoglucosan, mannosan, galactosan) were detected in all charred samples. The comparison of charred and uncharred samples allowed the identification of unaltered pine derived biomolecules and their thermal alteration products in the charred samples. Terpenoid and steroid biomolecules were in part altered during incomplete combustion to aromatic, unsaturated and polar derivatives (“pyromolecules”) that still retained the characteristic skeleton of their precursors. Since some of the polar degradation products found in the charred soils can be generated either from thermal or microbial degradation, the aromatic and unsaturated hydrocarbon products are preferred as molecular markers for SOM burning. Ratios of biological precursors to aromatic (diterpenoids) or unsaturated products (steroids) indicate that the cyclic lipids in the pine wood and the soil surface horizon were highly altered. In conclusion, the solvent extractable lipids and carbohydrates in charred SOM are valuable, source-specific molecular markers for the burning of plant biomass and for tracing the biogeochemistry of charred residues in soils.     

Characterization of natural organic matter in bentonite clays for potential use in deep geological repositories for used nuclear fuel

The Nuclear Waste Management Organization (NWMO) is developing a Deep Geological Repository (DGR) to contain and isolate used nuclear fuel in a suitable rock formation at a depth of approximately 500 m. The design concept employs a multibarrier system, including the use of copper-coated used fuel containers, surrounded by a low-permeability, swelling clay buffer material within a low permeability, stable host rock environment. The natural organic matter (NOM) composition of the bentonite clays being considered for the buffer material is largely uncharacterized at the molecular-level. To gain a better understanding of the NOM in target clays from Wyoming and Saskatchewan, molecular-level methods (biomarker analysis, solid-state ¹³C NMR and solution-state ¹H nuclear magnetic resonance (NMR)) were used to elucidate the structure and sources of NOM. Organic carbon content in three commercially available bentonites analyzed was low (0.11–0.41%). The aliphatic lipid distribution of the clay samples analyzed showed a predominance of higher concentration of lipids from vascular plants and low concentrations of lipids consistent with microbial origin. The lignin phenol vanillyl acid to aldehyde ratio (Ad/Al) for the National sample indicated an advanced state of lignin oxidation and NOM diagenesis. The ¹³C NMR spectra were dominated by signals in the aromatic and aliphatic regions. The ratio of alkyl/O-alkyl carbon ranged from 7.6 to 9.7, indicating that the NOM has undergone advanced diagenetic alteration. The absence lignin-derived phenols commonly observed in CuO oxidation extracts from contemporary soils and sediments as well as the lack of amino acids suggests that the material corresponding to the aromatic signal is not composed of lignin or proteins but may be derived from another source such as black carbon or some other non-extractable aromatic-rich NOM. The aliphatic signal appears to correspond to long-chain compounds with little side branching based on the results of the one-dimensional (1D) and two-dimensional (2D) solution-state ¹H NMR analyses. Overall, the organic geochemical analyses suggest that the NOM is composed mainly of plant-derived waxes and highly aromatic carbon with low contributions from small molecules. The compounds identified by the molecular-level analysis of NOM in the clay samples are hypothesized to be recalcitrant but future studies should examine if these compounds may serve as a microbial substrate to further test the observations of this study. Furthermore, our study suggests that the NOM has undergone diagenesis and that marine NOM signatures are no longer recognizable or detectable. As such, future work may also examine the diagenesis of these deposits to further understand the NOM geochemistry and paleoenvironmental conditions in bentonite deposits.     

Assessing the fate and transformation of plant residues in the terrestrial environment using HR-MAS NMR spectroscopy

Plant litter decomposition plays a fundamental role in carbon and nitrogen cycles, provides key nutrients to the soil environment and represents a potentially large positive feedback to atmospheric CO₂. However, the full details of decomposition pathways and products are unknown. Here we present the first application of HR-MAS NMR spectroscopy on ¹³C and ¹⁵N labeled plant materials, and apply this approach in a preliminary study to monitor the environmental degradation of the pine and wheatgrass residues over time. In HR-MAS, is it possible to acquire very high resolution NMR data of plant biomass, and apply the vast array of multidimensional experiments available in conventional solution-state NMR. High levels of isotopic enrichment combined with HR-MAS significantly enhance the detection limits, and provide a wealth of information that is unattainable by any other method. Diffusion edited HR-MAS NMR data reveal the rapid loss of carbohydrate structures, while two-dimensional (2-D) HR-MAS NMR spectra demonstrate the relatively fast loss of both hydrolysable and condensed tannin structures from all plant tissues studied. Aromatic (partially lignin) and aliphatic components (waxes, cuticles) tend to persist, along with a small fraction of carbohydrate, and become highly functionalized over time. While one-dimensional (1-D)¹³C HR-MAS NMR spectra of fresh plant tissue reflect compositional differences between pine and grass, these differences become negligible after decomposition suggesting that recalcitrant carbon may be similar despite the plant source. Two-dimensional ¹H-¹⁵N HR-MAS NMR analysis of the pine residue suggests that nitrogen from specific peptides is either selectively preserved or used for the synthesis of what appears to be novel structures. The amount of relevant data generated from plant components in situ using HR-MAS NMR is highly encouraging, and demonstrates that complete assignment will yield unprecedented structural knowledge of plant cell components, and provide a powerful tool with which to assess carbon sequestration and transformation in the environment.     

Diagenesis of organic matter in a 400 m organic rich sediment core from offshore Namibia using solid state 13C NMR and FTIR

Although rates and mechanisms of early diagenesis have been well studied, the effects of microbial metabolism on the molecular composition of the sedimentary organic matter (SOM) over long periods of time need more investigation. In this study, we characterize the early diagenesis of marine SOM from organic rich sediments of the Ocean Drilling Program site 1082 located off Namibia, in the vicinity of the Benguela coastal upwelling system. We used both Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C NMR) to assess the quantitative partitioning of the organic carbon into major compound classes (aliphatic, aromatic, ester, carboxylic, amide and carbons from carbohydrates). Then, we calculate the SOM composition in the main biomolecules (proteins, carbohydrates, lipids and lignin) on the basis of previous ¹³C NMR based estimates of the molecular composition of the organic mixtures. Results show that the SOM is still labile at 7 m below the seafloor (mbsf) and composed of about 25% proteins and 15% carbohydrates. With increasing depth, the protein content exponentially decreases to 13% at 367 mbsf, whereas the carbohydrate content decreases linearly to 11%. The lignin and lipid content consistently represent around 10% and 40% of the SOM, respectively, and show an increase with depth, due mostly to selective enrichment as the more labile components are lost by degradation. Thus, these components of the SOM are considered refractory at the depth scale considered. The calculated remineralization rates are extremely slow ranging from 5.6 mol C m⁻³ ky⁻¹ at the top of the core to 0.2 mol C m⁻³ ky⁻¹ according to the organic carbon flux to the seafloor. Knowing the labile carbon losses, we propose a method to calculate the initial TOC before the diagenesis took place.     

A study of lignin degradation in leaf and needle litter using C-labelled tetramethylammonium hydroxide (TMAH) thermochemolysis: Comparison with CuO oxidation and van Soest methods

We studied the degradation of lignin in leaf and needle litter of ash, beech, maple, pine and spruce using ¹³C-labelled tetramethylammonium hydroxide (¹³C TMAH) thermochemolysis. Samples were allowed to decompose for 27 months in litter bags at a German spruce forest site, resulting in a range of mass loss from 26% (beech) to 58% (ash). In contrast to conventional unlabelled TMAH thermochemolysis, ¹³C-labelling allows thermochemolysis products from lignin, demethylated lignin and other polyphenolic litter compounds (e.g. tannins) to be distinguished. Proxies for lignin degradation (phenol yield; acid/aldehyde ratio of products) changed considerably upon correction for the contribution of non-lignin sources to the thermochemolysis products. Using the corrected values, we found increasing acid/aldehyde values as well as decreasing or constant yield of lignin derived phenols normalised to litter carbon, suggesting pronounced lignin degradation by wood-rotting fungi. No indication for build up of demethylated lignin through the action of brown rot fungi on ring methoxyls was found. The results were compared with those of other analytical techniques applied in previous studies. Like ¹³C-TMAH thermochemolysis, CuO oxidation showed increasing lignin oxidation (acid/aldehyde ratio) and no/little enrichment of lignin derived phenols in the litter. Molecular lignin degradation patterns did not match those from analysis of total acid unhydrolysable residues (AURs). In particular, the long assumed selective preservation of lignin during the first months of litter decomposition, based on AUR analysis, was not supported by results from the CuO and ¹³C TMAH methods.     

Relative contribution of foliar and fine root pine litter to the molecular composition of soil organic matter after in situ degradation

The influence of litter quality on soil organic matter (SOM) stabilization rate and pathways remains unclear. We used ¹³C/¹⁵N labeled litter addition and Curie-point pyrolysis gas chromatography–mass spectrometry combustion-isotope ratio mass spectrometry (Py–GC–MS–C–IRMS) to explore the transformation of litter with different composition and decay rate (ponderosa pine needle vs. fine root) to SOM during 18 months in a temperate conifer forest mineral (A horizon) soil. Based on ¹³C Py–GC–MS–C–IRMS the initial litter and bulk soil had ∼1/3 of the total pyrolysis products identified in common. The majority was related either to carbohydrates or was non-specific in origin. In bulk soil, carbohydrates had similar levels of enrichment after needle input and fine root input, while the non-specific products were more enriched after needle input. In the humin SOM fraction (260 yr C turnover time) we found only carbohydrate and alkyl C-derived compounds and greater ¹³C enrichment in the “carbohydrate” pool after fine root decomposition. ¹⁵N Py–GC–MS–C–IRMS of humic substances showed that root litter contributed more than needle litter to the enrichment of specific protein markers during initial decomposition.We found little evidence for the selective preservation of plant compounds considered to be recalcitrant. Our findings suggest an indirect role for decomposing plant material composition, where microbial alteration of fine root litter seems to favor greater initial stabilization of microbially derived C and N in SOM fractions with long mean turnover times, such as humin, compared to needles with a faster decay rate.     

Molecular composition of sedimentary humic acids from South West Iberian Peninsula: A multi-proxy approach

The molecular structural features of humic acid (HA) fractions isolated from recent sediments from the estuaries and continental platform along the Huelva littoral (SW Iberian Peninsula, Spain) were studied using complementary analytical tools. The approach included elemental analysis, solid state, ¹³C cross polarisation magic angle spinning nuclear magnetic resonance spectroscopy (¹³C CP-MAS NMR), pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) and stable C and N isotopic composition (δ¹³C, δ¹⁵N). The results point to the presence of vascular plant matter contributing to all the HAs, even those far from the coastal area. A contribution of lignocellulose material was detected from ¹³C NMR signals at 152 ppm (O-aryl C), 55 ppm (methoxyl C) and 33 ppm (alkyl chain) and confirmed by the presence of lignin derived structures (methoxy phenols) in the pyrolysis chromatograms. Nevertheless, the HAs from the westernmost part of the continental platform had the lowest aromatic and the highest C-alkyl abundance (¹³C NMR spectroscopy). These data, combined with low C/N and high H/C values, a relative enrichment in δ¹³C and the presence in the pyrolysates of conspicuous n-alkyl nitrile and amide series, together with n-alkane/ene homologues, pointed towards a relevant marine (autochthonous) contribution to this sedimentary organic matter (OM). In contrast, HAs from sediments collected from the Tinto-Odiel River mouth and Guadiana Estuary areas revealed a major input of terrestrial OM. In general, the data support the idea that the HAs still contain valuable information about the signature of aliphatic and aromatic biomacromolecules contributing to the deposited OM.     

Biogeochemistry of mineral-organic associations across a long-term mineralogical soil gradient (0.3-4100 kyr), Hawaiian Islands

Organic matter (OM) in mineral-organic associations (MOAs) represents a large fraction of carbon in terrestrial ecosystems which is considered stable against biodegradation. To assess the role of MOAs in carbon cycling, there is a need to better understand (i) the time-dependent biogeochemical evolution of MOAs in soil, (ii) the effect of the mineral composition on the physico-chemical properties of attached OM, and (iii) the resulting consequences for the stabilization of OM. We studied the development of MOAs across a mineralogical soil gradient (0.3-4100 kyr) at the Hawaiian Islands that derived from basaltic tephra under comparable climatic and hydrological regimes. Mineral-organic associations were characterized using biomarker analyses of OM with chemolytic methods (lignin phenols, non-cellulosic carbohydrates) and wet chemical extractions, surface area/porosity measurements (N₂ at 77 K and CO₂ at 273 K), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results show that in the initial weathering stage (0.3 kyr), MOAs are mainly composed of primary, low-surface area minerals (olivine, pyroxene, feldspar) with small amounts of attached OM and lignin phenols but a large contribution of microbial-derived carbohydrates. As high-surface area, poorly crystalline (PC) minerals increase in abundance during the second weathering stage (20-400 kyr), the content of mineral-associated OM increased sharply, up to 290 mg C/g MOA, with lignin phenols being favored over carbohydrates in the association with minerals. In the third and final weathering stage (1400-4100 kyr), metastable PC phases transformed into well crystalline secondary Fe and Al (hydr)oxides and kaolin minerals that were associated with less OM overall, and depleted in both lignin and carbohydrate as a fraction of total OM. XPS, the N₂ pore volume data and OM-mineral volumetric ratios suggest that, in contrast to the endmember sites where OM accumulated at the surfaces of larger mineral grains, topsoil MOAs of the 20-400-kyr sites are composed of a homogeneous admixture of small-sized PC minerals and OM, which originated from both adsorption and precipitation processes. The chemical composition of OM in surface-horizon MOAs, however, was largely controlled by the uniform source vegetation irrespective of the substrate age whereas in subsoil horizons, aromatic and carboxylic C correlated positively with oxalate-extractable Al and Si and CuCl₂-extractable Al concentrations representing PC aluminosilicates and Al-organic complexes (r² > 0.85). Additionally, XPS depth profiles suggest a zonal structure of sorbed OM with aromatic carbons being enriched in the proximity of mineral surfaces and amide carbons (peptides/proteins) being located in outer regions of MOAs. Albeit the mineralogical and compositional changes of OM, the rigidity of mineral-associated OM as analyzed by DSC changed little over time. A significantly reduced side chain mobility of sorbed OM was, however, observed in subsoil MOAs, which likely arose from stronger mineral-organic bindings. In conclusion, our study shows that the properties of soil MOAs change substantially over time with different mineral assemblages favoring the association of different types of OM, which is further accentuated by a vertical gradient of OM composition on mineral surfaces. Factors supporting the stabilization of sorbed OM were (i) the surface area and reactivity of minerals (primary or secondary crystalline minerals versus PC secondary minerals), (ii) the association of OM with micropores of PC minerals (via ‘sterically’ enhanced adsorption), (iii) the effective embedding of OM in ‘well mixed’ arrays with PC minerals and monomeric/polymeric metal species, (iv) the inherent stability of acidic aromatic OM components, and (iv) an impaired segmental mobility of sorbed OM, which might increase its stability against desorption and microbial utilization.     

Wetland soil organic matter composition in a Mediterranean semiarid wetland (Las Tablas de Daimiel, Central Spain): Insight into different carbon sequestration pathways

Wetland soils from a Mediterranean semiarid wetland (Las Tablas de Daimiel, Central Spain) were studied to characterize the organic matter (OM) and determine its origin and transformation. Cross polarization magic angle spinning (CPMAS) ¹³C nuclear magnetic resonance (NMR) spectroscopy and mathematical molecular mixing allowed analysis of the organic fraction in terms of six generic components (carbohydrate, protein, lignin, lipid, char and “carbonyl”). Las Tablas is an active carbon sink, with total organic carbon (TOC) content independent of soil OM quality; the TOC content of the upper sediment is 10.0 ± 7.8%. The inorganic carbon content is also high (5.4 ± 3.3%) and is associated mainly with OM of aliphatic character. The OM composition is variable; samples predominantly aliphatic (carbohydrate, lipid and protein) are characteristic of the northern sector, whereas predominantly aromatic samples are typical of the southern Tablas. A strong negative relationship between protein content and lignin content was found, interpreted as a consequence of different proportions of vascular vs. non-vascular (mostly charophyte) litter input. The effect of perturbation is apparent in the extended presence of char, particularly abundant in fire-prone areas. OM quantity and quality do not seem to depend on hydrology (although seasonal flooding is associated with lower TOC wetland soils) or soil characteristics. Dominant vegetation and fire are the main drivers of OM content and composition. Structural carbohydrate, protein and lipid (>60% of total organic fraction) dominate. Widespread anaerobic conditions and the recent character of the sediments could explain the preservation of different fractions of the original detritus composition (due to different vegetation and presence of microbes).     

Association of specific organic matter compounds in size fractions of soils under different environmental controls

Inherent chemical recalcitrance and association of organic matter (OM) with minerals are mechanisms responsible for the long term preservation of OM in soils. The structural characteristics of OM are also believed to control specific interactions between OM and soil minerals. However, the extent of the relationship between recalcitrance and mineral protection and the specificity of these chemically driven interactions are not clearly understood at the molecular level. To measure chemical patterns of OM sequestration in sand-, silt-, clay-size and light fractions, we analyzed three soils, which mainly differed in carbon content and overlying vegetation, but have similar clay mineralogy, using biomarker analysis and nuclear magnetic resonance (NMR). Despite differences in environmental controls, long chain aliphatic compounds generally accumulated in the fine fractions of all soils. This accumulation is likely due to the strong interaction between recalcitrant forms of OM and soil minerals. For example, polymethylene and >C₂₀ organic acids accumulated in fine fractions, while lignin-derived phenols were protected from oxidation in silt-size fractions. Diffusion edited solution state ¹H NMR suggested that contributions from microbial-derived OM was greater in finer fractions, which is likely due to the accumulation of microbial-derived compounds or higher microbial activity in clay micro-sites. Our data suggest that, for these Prairie soils, the specific structure of OM and not environmental factors is responsible for long term preservation of OM in mineral fractions. Further research is necessary to understand the interplay between these preservation mechanisms such that the long term fate of OM can be further elucidated.     

9000 years of changes in peat organic matter composition in Store Mosse (Sweden) traced using FTIR-ATR

Store Mosse (the ‘Great Bog’ in Swedish) is one of the most extensive bog complexes in southern Sweden (~77 km²), where pioneering palaeoenvironmental research has been carried out since the early 20th century. This includes, for example, vegetation changes, carbon and nitrogen dynamics, peat decomposition, atmospheric metal pollution, mineral dust deposition, dendrochronology, and tephrochronology. Even though organic matter (OM) represents the bulk of the peat mass and its compositional change has the potential to provide crucial ecological information on bog responses to environmental factors, peat OM molecular composition has not been addressed in detail. Here, a 568-cm-deep peat sequence was studied at high resolution, by attenuated reflectance Fourier-transform infrared spectroscopy (FTIR-ATR) in the mid-infrared region (4000–400 cm^–1). Principal components analysis was performed on selected absorbances and change-point modelling was applied to the records to determine the timing of changes. Four components accounted for peat composition: (i) depletion/accumulation of labile (i.e. carbohydrates) and recalcitrant (i.e. lignin and other aromatics, aliphatics, organic acids and some N compounds) compounds, due to peat decomposition; (ii) variations in N compounds and carbohydrates; (iii) residual variation of lignin and organic acids; and (iv) residual variation of aliphatic structures. Peat decomposition showed two main patterns: a long-term trend highly correlated to peat age (r = 0.87), and a short-term trend, which showed five main phases of increased decomposition (at ~8.4–8.1, ~7.0–5.6, ~3.5–3.1, ~2.7–2.1 and ~1.6–1.3 ka) – mostly corresponding to drier climate and its effect on bog hydrology. The high peat accumulation event (~5.6–3.9 ka), described in earlier studies, is characterized by the lowest degree of peat decomposition of the whole record. Given that FTIR-ATR is a quick, non-destructive, cost-effective technique, our results indicate that it can be applied in a systematic way (including multicore studies) to peat research and provide relevant information on the evolution of peatlands.     

Early coalification features as approached by solid state C CP/MAS NMR spectroscopy

Solid state ¹³C CP/MAS NMR spectroscopy and ultimate analysis have been applied to a study of samples from the Pleistocene Drama lignite and its successive modern analogue, the Philippi peat, in northeastern Greece. The succession from peat to lignite resulted in a C enrichment averaging 10.7% and depletion in H and O averaging 6.5 and 18.5%, respectively. Early coalification resulted in the degradation of methoxyl groups, carbohydrates and carboxylic groups, whereas the aliphatic carbons were less affected. However, organic geochemical alteration seems to depend strongly on the initial peatification conditions. The “aromaticity” decreases from the stage of peat to lignite, as a result of the significant degradation of lignin precursors.     

Comparison of the structures of humic substances from aquatic and terrestrial sources by pyrolysis gas chromatography-mass spectrometry

Four humic extracts isolated from terrestrial, mahne, plankton and freshwater sources have been investigated by pyrolysis-gas chromatography-mass spectrometry. The results show that substantial quantities of phenols (some not derived from lignin), pyrroles and nitrites (derived from proteins, nucleic acids or porphyrins) are decomposition products. Small amounts of furans (derived from carbohydrates) and unsaturated ketones (derived from polycarboxylic aliphatic acids) are also present. The results illustrate how parent material, transport factors and biological activity affect the composition of humic extracts.     

Early diagenesis of carbohydrates and lignin in mangrove sediments subject to variable redox conditions (French Guiana)

A comparative study of lignin and neutral carbohydrate compositions, combined with C, N and δ¹³C analyses, was carried out on sedimentary cores, and on various vascular plant species collected in mangrove swamps of French Guiana. The main purpose of this study was to assess the diagenesis of carbohydrates and lignin in brackish to hypersaline fine-grained mangrove sediments characterized by great changes in redox conditions. Distribution of carbohydrates in sediments reflects both the lability of these compounds and their efficient recycling. They are subject to selective degradation, cellulosic glucose and xylose appearing to be the two most labile neutral sugars. In contrast a relative increase in arabinose, rhamnose, fucose and hemicellulosic glucose between plants and sediments, suggests that they may be more refractory and/or that they also derive from microbial synthesis. The total carbon from lignin-derived phenols is higher in sediments than in mangrove plants as a consequence of their rather refractory character. Nevertheless, evidence of lignin decomposition was found to be independent of local environmental conditions. The various redox processes that occur in mangrove sediments depend on plant species, stages in forest development and season. Different redox conditions induce different mechanisms for the decomposition of lignin and thus induce changes in phenol distributions. At depth, in most mangroves, an increase in (Ad/Al)_v ratios and in deoxy sugars (fucose and rhamnose) content was significantly correlated with increased proportions of oxidized allochthonous organic debris deriving from the Amazonian detrital discharge, thus suggesting a specific source effect rather than a diagenesis induced change. Therefore, this study illustrates that both lignin and cellulose, derived from vascular plant debris, can be degraded in waterlogged mangrove sediments, and that their distribution depends on environmental conditions.     

A 35 kyr record of organic matter composition and δ13C of n-alkanes in bog sediments close to Lake Baikal: Implications for paleoenvironmental studies

We characterized the compositions of organic compounds in a Cheremushka bog sediment core (deposited over the last 35 kyr), located at the eastern coast of Lake Baikal, to obtain basic information about the terrestrial organic matter (OM) which contributed to Lake Baikal sediments. The bog sediment was analyzed for the molecular composition of n-alkanes, lignin phenols and n-C₂₄ to C₃₀ alkanoic acids, as well as the carbon isotopic composition of plant wax derived n-C₂₇ to C₃₃ alkanes.Concentrations of lignin phenols [vanillyl (V) plus syringyl (S) phenols] normalized to total organic carbon (TOC) in the Holocene are twice those for the last glacial maximum (LGM), while concentrations of TOC-normalized n-C₂₄ to C₃₀ alkanoic acids do not change markedly in this period. Thus, the ratio of lignin phenols to n-C₂₄ to C₃₀ alkanoic acids increases from the LGM to the Holocene. This result is essentially consistent with pollen analysis indicating an expansion of woody plants in the Holocene and a prevailing herb-abundant environment for the LGM. The δ¹³C values of n-C₂₇ to C₃₃ alkanes (e.g. ?29‰ to ?33‰ for C₃₁) indicate the presence of C₃-dominant plants throughout the core.The contribution of terrestrial OM to Lake Baikal sediments was estimated using the biomarkers, on the assumption that the OM in the bog sediments is a representative of the terrestrial OM around the lake. Hence, the estimation using lignin phenol or n-C₂₄ to C₃₀ alkanoic acid parameters indicates that 11–24% of the TOC in the Academician Ridge sediments is land-derived for both the Holocene and the LGM, which is similar to the estimates from C/N values of bulk OM. However, the estimates for terrestrial OM using the n-C₂₇ to C₃₃ alkane parameter are generally higher than those using lignin phenol or n-C₂₄ to C₃₀ alkanoic acid parameters. The difference is thought to be associated with the difference in source and behavior of these biomarkers.     

Recent vegetation history from a swampy environment to a pond based on macromolecular organic matter (lignin and fatty acids) and pollen sedimentary records

Evidence of environmental and vegetation changes in the catchment area of a small pond created artificially during the Middle Ages from a swampy area was provided by coupling palynology data and a detailed study of macromolecular organic matter (OM). Tetramethylammonium hydroxide (TMAH) thermochemolysis after solvent extraction was used to characterize macromolecular OM and particularly lignin and fatty acids (FAs). Molecular ratios such as TAR_(FA), C_16:1/C_16:0 and C_18:1/C_18:0 were calculated to characterize the FAs incorporated into the macromolecular OM. Moreover, syringyl vs. vanillyl phenols (S/V) and cinnamyl vs. vanillyl phenols (C/V) molecular ratios were investigated to fingerprint the lignin sources. These different markers suggested that the swampy area was dominated by a non-woody angiosperm input and gave rise to pond status over a period of several centuries. Indeed, TAR_(FA) correlated with the aquatic contribution, which became predominant after creation of the pond. The use of ratios of total acid phenols to the total aldehyde phenols of syringyl or vanillyl units (Ad/Al_(s), Ad/Al_(v)), which are related to the degree of oxidation of lignin, revealed the irregular operation of oxidative conditions.     

Physical protection of lignin by organic matter and clay minerals from chemical oxidation

The role of organic matter (OM) concentration, structure and composition and how these relate to mineral protection is important for the understanding of long term soil OM dynamics. Various OM–clay complexes were constructed by sequential sorption of lignin and dodecanoic acid to montmorillonite. Humic acid–montmorillonite complexes were prepared at pH 4 and 7 to vary OM conformation prior to sorption. Results obtained with constructed OM–clay complexes were tested with isolated mineral fractions from two soils. Oxidation with an acidic NaClO₂ solution was used to chemically oxidize lignin in the OM–clay complexes, sand-, silt- and clay-size soil fractions to test whether or not it can be protected from chemical attack. Gas chromatography–mass spectrometry was used to analyze lignin-derived phenols, cutin OH–acid (after CuO oxidation), fatty acid and n-alkanol concentrations and composition. We found that carbon content was not solely responsible for lignin stability against chemical oxidation. Lignin was protected from chemical oxidation through coating with dodecanoic acid and sorption of humic acid to clay minerals in a stretched conformation at pH 7. Therefore, interactions between OM constituents as well as OM conformation are important factors that protect lignin from chemical oxidation. Lignin-derived phenol dimers in the Grassland-Forest Transition soil fractions were protected from chemical oxidation to a greater extent compared to those in Grassland soil fractions. Therefore, although lignin was protected from degradation through mineral association, the extent of this protection was also related to OM content and the specific stability of lignin components.     

The degradation characteristics of microbial biomass in soil

Soil microbial biomass is a primary source of soil organic carbon (SOC) and therefore plays a fundamental role in carbon and nitrogen cycling. However, little is known about the fate and transformations of microbial biomass in soil. Here we employ HR-MAS NMR spectroscopy to monitor ¹³C and ¹⁵N labeled soil microbial biomass and leachate degradation over time. As expected, there is a rapid loss of carbohydrate structures. However, diffusion edited HR-MAS NMR data reveals that macromolecular carbohydrates are more resistant to degradation and are found in the leachate. Aromatic components survive as dissolved species in the leachate while aliphatic components persist in both the biomass and leachate. Dissolved protein and peptidoglycan accumulate in the leachate and recalcitrant amide nitrogen and lipoprotein persists in both the degraded biomass and leachate. Cross-peaks that appear in ¹H-¹⁵N HR-MAS NMR spectra after degradation suggest that specific peptides are either selectively preserved or used for the synthesis of unknown structures. The overall degradation pathways reported here are similar to that of decomposing plant material degraded under similar conditions suggesting that the difference between recalcitrant carbon from different sources is negligible after decomposition.