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Background We applied Fourier-Transformed Infrared Spectroscopy (FTIR) techniques in combination with selective humus extractions to investigate in situ the chemical features of organic matter in three soil profiles recently developed from Dutch sand dunes, under well-documented vegetation sequence and containing a relatively simple mineral-organic matter system. Water-soluble and alkaline-soluble extracts were also studied to match the changes of humus in the soil residues. Results Diffuse Reflectance Infrared Fourier Transform (DRIFT) and transmission spectra differed in resolution and sensitivity. DRIFT was superior in revealing structural information on the organic matter present in the soil samples whereas transmission spectra showed higher resolution for the bands of inorganic material at lower spectral frequencies. Differences between H and B horizons were due to the amount of hydrophilic organic acids, partly unsaturated, that were extracted by alkali. Extractable carboxylic acids and other hydrophilic compounds such as peptides and carbohydrates were larger in the less developed soils under pine and crowberry than in the more advanced profiles under beech. Humin residues from both H and B horizons retained unextractable aliphatic components and carboxylic groups involved in strong complexes with minerals, thereby confirming other findings that showed the largely aliphatic character of the unextractable humic fraction. Accumulation of poorly-soluble organic materials in these soils occur by protection from biodegradation due both to complexation with soil minerals and to a process by which apolar humic constituents form a separate hydrophobic phase where no biological activity can take place. Transport of poorly soluble compounds from H to B horizons, noticed especially in the more developed profiles, may have occurred through humic aggregates containing hydrophobic phases. Conclusions This work shows that the DRIFT technique in combination with soil chemical treatments can be suitably employed to investigate the changes of organic matter in whole soil samples and represents a valid tool to investigate the role of organic matter in soil profile development.

In podzols important environmental issues converge, including dissolved organic matter (DOM) transport, DOM-metal binding, and carbon storage in the subsoil. Therefore, it is important to understand the formation and degradation of podzols in relation to (changes in) environmental conditions. For this purpose a Holocene barrier island with coastal sand dunes (Ilha Comprida, SE Brazil) was chosen as study area. The island is build-up of five geomorphic units that have different age (from >5000 to 325 y BP), vegetation (restinga ecosystems), soil hydrology (flat units or units with ridges and swales) and drainage (poorly drained, well-drained, and improved drainage). Representative profiles were studied for each geomorphic unit, resulting in 100 samples from A, E, B, and C horizons, from which soil organic matter (SOM) was isolated by alkaline extraction. To better understand carbon sources and dynamics, we additionally sampled litter from different vegetation types and DOM from various sources. The molecular composition of SOM, DOM and litter was analyzed with pyrolysis gas chromatography mass spectrometry (pyrolysis-GC/MS). Comparing the pyrolysates of all samples (DOM, SOM and litter) factor analysis demonstrated that the major difference in molecular composition (factor 1) was related to the contribution from DOM (phenol, acetic acid, benzofurans, pyridine, benzene and naphthalene) or in-situ root material (straight chain aliphatics and methoxyphenols from the biomacromolecules suberan and lignin, respectively). The contribution from DOM or roots was characteristic for a profile i.e. without much change with depth. Factor 2 reflected decomposition processes, and showed that the predominantly DOM-derived B horizons were relatively enriched in aromatics compared to DOM, indicating selective decay and/or selective precipitation. In geomorphic units with swales and ridges that received DOM via groundwater flow from the catchment area, the B horizon was predominantly DOM-derived; these profiles showed large differences in the contribution from black carbon (BC; (poly)aromatics), with the younger profiles showing a larger contribution from BC in precipitated DOM. B horizons with a relatively large contribution from in-situ root materials were found in well-drained soils and in some of the poorly drained soils without lateral groundwater flow from the catchment area, i.e., the flat geomorphic unit without ridges and swales. Microbial material (N-containing compounds and sugars) was associated with relatively recent SOM and with well-drained conditions at present. i.e., well-drained profiles, and profiles with improved drainage.

Morphology of podzol profiles can be used to improve our understanding of soil formation and degradation processes. The morphology of a podzol chronosequence was studied for a 1800 m long cliff perpendicular to the coastline at the southern coast of the Island Ilha Comprida (Sao Paulo, Brazil). The large variation in hydrological conditions with time (surfaces with ages from 6000 to 300 yrs BP) and space (topography) allowed studying the relation between podzol morphology and drainage conditions, both during soil formation and degradation. On the oldest two surfaces, the podzols formed under poorly drained circumstances. Uplift during their formation resulted in (1) very deep Bh horizons and (2) degradation of the upper B horizon as a result of improved drainage. On the younger surface most podzols were poorly drained, but well-drained podzols and transitions occurred in beach ridges. In the cliffs on the southern coast of the island, improved drainage of the poorly drained podzols resulted in degradation of the B horizon. This degradation exhibits various forms, including (1) complete removal of the B horizon down to an underlying clay layer, (2) degradation of the B horizon along root channels with preferential vertical water transport, (3) degradation of the upper B horizon resulting in a diffuse EB transition, and (4) areas of organic matter (OM) depletion related to microbial activity, sometimes combined with burrowing. Type (2) degradation may result in a convoluted EB transition, the formation of islands of B horizon in the deepening E horizon, and formation of E horizon tongues into the Bh. Recent (post degradation) OM bands were found in E and B horizons. A thorough study of podzol morphology can be used to reconstruct several stages of their formation and degradation in relation to drainage conditions.

Important parameters that influence biochar properties include charring temperature and biomass type. We characterized the molecular properties of biochars from five agricultural residues with pyrolysis gas chromatography mass/spectrometry (pyrolysis-GC/MS) in comparison with atomic H/C and N/C ratios. Feedstocks included chicken manure, eucalyptus sawdust, coffee husk, sugarcane bagasse and pine bark. Biochars produced at three different temperatures (Tchar) were analyzed, including 350, 450 and 750 °C, as well as the uncharred materials. The optimum temperature during analysis with pyrolysis-GC/MS (Tpy) was examined. Tpy 600 °C gave the best results for all Tchar by showing a larger diversity of pyrolysis products compared to Tpy 700 °C and 800 °C; Tpy 600 °C was therefore used for qualitative and quantitative comparison of the samples. Charring temperature was the dominant factor that determined the chemical composition of the biochar pyrolysates. Uncharred feedstocks had the largest contribution from carbohydrates, lignin phenols and long chain n-alkanes, all of which rapidly decreased with charring; biochars produced at Tchar 350 and 450 °C showed the largest contribution from phenols, mid-chain n-alkanes, benzofurans, indenes, biphenyls and PAHs, from which the benzofurans, indenes, biphenyls and PAHs were particular abundant in samples produced at Tchar 450 °C; pyrolysates of biochars produced at Tchar 750 °C were characterized by branched aliphatics, short chain n-alkanes/n-alkenes and low molecular weight (LMW) benzenes. Factor analysis showed that the variation of products differed largely within some chemical groups. For the N-containing compounds, caffeine, C16 alkylnitrile and diketopiperazines were associated with uncharred materials, benzonitriles and quinolines were associated with Tchar 350–450 °C. Another part of the variation of N-containing compounds was associated with chicken manure, and to a lesser extend also coffee husk, independently of Tchar. For all five agricultural residues, the highest chemical diversity was found for biochar produced at Tchar 350 °C. As the charring temperature increased, the diversity of pyrolysis products diminished.

The occurrence of dark subsurface horizons rich in organic matter (OM) associated with polychrome in the B horizon (yellowish over reddish hue) is common in soils from Southern Brazil. The formation of these horizons and the combination with such morphological attributes has not been properly documented, and neither has the cause effect relationship. Four soil profiles with such sombric-like horizons with a yellowish color at the upper part of the B horizon over red subsoil were studied in Southern Brazil. Results from micromorphology, extractable sesquioxide minerals, clay mineralogy and isomorphic substitution of Fe by Al in iron minerals showed that melanization, xanthization, bioturbation, moderate shrinking/swelling and moderate ferralitization were the most evident pedogenetic processes in role. Xanthization is closely related to the sombric-like horizon formation. In the studied area the findings demonstrated that no clay and OM illuviation had taken place. Therefore, the classification of these soils was revisited, so as to take into account the processes that underlie their genesis with emphasis on xanthization, clay illuviation and soil aggregation. The results suggest that the sombric horizon may need redefinition, unless profiles can be found in which illuviation of clay and/or OM can be proven.

The occurrence of Umbric Ferralsols with thick umbric epipedons (> 100 cm thickness) in humid Tropical and Subtropical areas is a paradox since the processes of organic matter decomposition in these environments are very efficient. Nevertheless, this soil type has been reported in areas in the Southeast and South of Brazil, and at some places in the Northeast. Aspects of the genesis and paleoenvironmental significance of these Ferralsols still need a better understanding. The processes that made the umbric horizons so thick and dark and contributed to the preservation of organic carbon (OC) at considerable depths in these soils are of special interest. In this study, eight Ferralsols with a thick umbric horizon (UF) under different vegetation types were sampled (tropical rain forest, tropical seasonal forest and savanna woodland) and their macromorphological, physical, chemical and mineralogical properties studied to detect soil characteristics that could explain the preservation of high carbon amounts at considerable depths. The studied UF are clayey to very clayey, strongly acidic, dystrophic, and Al-saturated and charcoal fragments are often scattered in the soil matrix. Kaolinites are the main clay minerals in the A and B horizons, followed by abundant gibbsite and hydroxyl-interlayered vermiculite. The latter was only found in UFs derived from basalt rock in the South of the country. Total carbon (TC) ranged from 5 to 101 g kg-1 in the umbric epipedon. Dichromate-oxidizable organic carbon represented nearly 75 % of TC in the thick A horizons, while non-oxidizable C, which includes recalcitrant C (e.g., charcoal), contributed to the remaining 25 % of TC. Carbon contents were not related to most of the inorganic soil variables studied, except for oxalate-extractable Al, which individually explained 69 % (P < 0.001) of the variability of TC in the umbric epipedon. Clay content was not suited as predictor of TC or of the other studied C forms. Bulk density, exchangeable Al3+, Al saturation, ECEC and other parameters obtained by selective extraction were not suitable as predictors of TC and other C forms. Interactions between organic matter and poorly crystalline minerals, as indicated by oxalate-extractable Al, appear to be one of the possible organic matter protection mechanisms of these soils. A ocorrência de Latossolos com horizonte A húmico hiperdesenvolvido (> 100 cm de espessura) nos trópicos e subtrópicos úmidos é um paradoxo, pois os processos de decomposição da matéria orgânica nesses ambientes são bastante eficientes. Apesar disso, esses solos têm sido documentados nas regiões Sudeste e Sul do Brasil, com algumas ocorrências na região Nordeste. Aspectos da gênese e do significado paleoambiental desses Latossolos aguardam por melhor entendimento. Os processos que levaram o horizonte A a ser tão espesso e escuro e contribuíram para preservação de C orgânico (CO) em profundidades consideráveis nesses pedons são de especial interesse. Neste trabalho, oito Latossolos com horizonte A húmico hiperdesenvolvido (Lh) sob diferentes fitofisionomias (Floresta Ombrófila, Floresta Estacional e Savana Arborizada) foram amostrados e os seus atributos macromorfológicos, físicos, químicos e mineralógicos estudados, com o objetivo de relacioná-los com a preservação de CO em profundidade. Esses Lh são argilosos a muito argilosos, fortemente ácidos, distróficos, álicos e muitos possuem fragmentos de carvão vegetal dispersos na matriz do solo. Caulinita é o principal mineral da fração argila nos horizontes A e B, seguido em abundância por gibbsita e por vermiculita com hidroxi entrecamadas. Este último argilomineral é identificado apenas nos Lh derivados de rochas basálticas da região Sul. Os teores de C total (CT) variam de 5 a 101 g kg-1 no horizonte A húmico. Carbono oxidado por via úmida com dicromato de potássio constitui, em média, 75 % do CT dos horizontes A húmicos, enquanto o C não oxidável com dicromato (C-res), que inclui formas de C recalcitrantes (como carvões), contribui para os restantes 25 % do CT. Os conteúdos de C foram independentes da maioria das variáveis inorgânicas do solo, exceto do Al extraído com oxalato de amônio ácido (OAA), que individualmente explica 69 % (P < 0,001) da variabilidade de CT do horizonte A húmico. Os conteúdos de argila não foram estimadores eficazes do CT e de outras formas de C estudadas, como também não foram: densidade do solo, Al3+ trocável, saturação por Al, capacidade de troca de cátions efetiva e outros parâmetros obtidos por extrações seletivas com OAA e ditionito-citrato-bicarbonato. Interações entre materiais orgânicos e minerais pobremente cristalinos, como indicado pelo Al extraído com OAA, apresentam-se como um dos mecanismos possíveis para proteção da matéria orgânica nesses solos.

Soil organic matter (OM) stability plays an important role in the global carbon cycle. The molecular characterisation of soil OM may contribute to an understanding of the feedback mechanisms between soil OM and climate. Umbric Ferralsols with humic properties (humic Ferralsols) are characterised by a thick dark carbon-rich A horizon, and co-occur next to Umbric Ferralsols without humic characteristics. They are concentrated in south-eastern Brazil which suggests an environmental control. In order to understand OM stability in these soils, humic Ferralsols from three Brazilian biomes were studied, including Cerrado (savanna), subtropical forest and tropical forest. The studied soils were developed on several geological substrates, including basalt, gneiss, chamokites, phyllite and tertiary sediments. The molecular composition of the free light fraction (FLF), occluded light fraction (OLF) and 0.1 M NaOH extractable OM of samples from topsoil and subsoil from eight profiles was examined using analytical pyrolysis (pyrolysis-GC/MS). The light fraction reflects litter and charcoal, obtained by density fractionation before (FLF) and after (OLF) ultrasonic disruption; the NaOH extractable fraction (humic acid + fulvic acid) reflects more decomposed material. The chemical differences among soils from different Brazilian biomes were much smaller than the vertical gradient within each profile. The results showed that, within the light fractions, the content of which varied between 2% and 22% of the total carbon content (C t ), black carbon (BC) derived pyrolysis products showed a higher abundance in the topsoil. In the extractable OM, which varied between 46% and 88% of C t , BC derived pyrolysis products showed a higher abundance in the subsoil. This suggests a continuous input of BC and an increase in the degree of decomposition with depth. Pyrolysis products associated with BC contributed up to 10% to the extractable pyrolysable fraction in the subsoil. The results suggest that degradation of charcoal, which is translocated to the subsoil by macroscopic soil organisms, results in a relative high contribution from naphthalene, 2-ethenylnaphthalene, phenanthrene, benzene, dibenzofuran and benzonitrile (subsoil) compared to (other) polyaromatic hydrocarbons (PAHs; C 1 -, C 2 - and C 3 -naphthalenes and fluorene) in relatively fresh charcoal (topsoil). The results highlight the importance of the subsoil in studies of the long term effects of fire on soil OM and suggest that BC is an important factor that underlies carbon stability in humic Ferralsols.

In archaeology and nature conservation studies, knowledge about (pre)historical land-use is important. The molecular composition of soil organic matter (SOM) supplies information about its history, as its composition is controlled by input material and decay processes. In this study, the molecular composition of SOM of calcareous A-horizons from SE Spain was studied with pyrolysis gas chromatography/mass spectrometry (pyrolysis-GC/MS). The effect of vegetation type (Pinus halepensis forest and Stipa tenacissima grassland), land-use (cultivation with cereals and olive trees) and wildfire were examined. In addition, former grassland and agricultural soils that had been reforested with P. halepensis (35 yr) were selected. Three locations were sampled for each vegetation type, except for the olive tree (two) and cereal (six) fields, resulting in a total of 26 samples. Each sample was a composite of ten sub-samples taken from a plot of 1 ha. After removal of weakly or non-decomposed particulate OM, two OM fractions were obtained; (i) sodium hydroxide (NaOH) extractable OM and (ii) the OM that remained after extraction, which was isolated after dissolution of minerals by repeated hydrofluoric acid (HF) treatment. The NaOH-extractable fraction is generally used in soil chemistry (i.e. humic acid), but surprisingly little is known about the SOM that remains in the residue (i.e. humin plus minerals). Comparison of the two SOM fractions (by factor analyses applied to 82 quantified pyrolysis products) provided insight into soil OM dynamics. Polyaromatic pyrolysis products were more prominent in the extractable OM, while a relative enrichment of aliphatic compounds was found in the non-extractable OM. Although some pyrolysis products were associated with one vegetation type in both SOM fractions (C3-naphthalene, dimethylphenanthrene and 2,3,5-trimethylphenanthrene, retene, and monoterpenes for both burnt and unburnt P. halepensis forest; benzene, naphthalene and C1-naphthalene for burnt and unburnt S. tenacissima grassland), lignin content and composition highly differed between agricultural soils and soils under native vegetation in both SOM fractions. These differences were mainly decay characteristics, reinforced by cultivation. In reforested soils it was still possible to identify their former land-use, decades after the vegetation change. The probability of the sites to be correctly attributed to its present land-use was P > 0.7 for grassland and pine forest, while most of the cultivated sites had a P > 0.5 to be assigned correctly. The results obtained suggest that the molecular composition of SOM has a large potential for reconstructing land-use history, at least at the scale of decades/centuries.

Insight in the molecular structure of humic acid (HA) and fulvic acid (FA) can contribute to identify relationships between their molecular properties, and further our quantitative abilities to model important organic matter functions such as metal complexation and association with mineral surfaces. Pyrolysis gas chromatography/mass spectrometry (Py-GC-MS) is used to compare the molecular composition of HA and FA. A systematic comparison was obtained by using samples from different environmental sources, including solid and aqueous samples from both natural and waste sources. The chemical signature of the pyrolysates was highly variable and no significant difference between HA and FA was found for major chemical groups, that is, carbohydrates, phenols, benzenes, and lignin phenols, together accounting for 62-96% of all quantified pyrolysis products. However, factor analysis showed that within each sample, FAs consistently differed from corresponding HAs in a larger contribution from mono- and polyaromatic hydrocarbons and heterocyclic hydrocarbons, together accounting for 3.9-44.5% of the quantified pyrolysis products. This consistent difference between FAs and corresponding HAs, suggests that their binding properties may, in addition to the carboxyl and phenolic groups, be influenced by the molecular architecture. Py-GC-MS may thus contribute to identify relationships between HA and FA binding- and molecular-properties.

The stability of soil organic matter (OM) in Amazonian anthropogenic soils, Terra Preta de Índio (TPI), is still not completely understood. The large contribution from black carbon (BC) and minerals to these soils is well-known; OM stability is therefore frequently explained by these properties, providing intrinsic recalcitrance (BC) and chemical protection against decomposition (OM-mineral associations), but the relative importance of both mechanisms that underlie the stability are not yet understood. In order to better understand the sources and decay processes of soil OM in these soils, we studied the molecular composition using pyrolysis gas-chromatography/mass-spectrometry. To this end, several soil OM fractions of samples from two TPI soils and an adjacent Xanthic Acrisol that served as a reference soil (REF) were studied (0–2 m depth). A sequential fractionation was applied in order to better understand the composition of soil OM pools with different association to the soil matrix. The studied soil OM fractions included the free light fraction (FLF; i.e., charcoal and litter), the occluded light fraction (OLF; charcoal and litter within aggregates), 0.1 M NaOH extractable OM (EX; comparable with the combined humic acid and fulvic acid fractions), and the remaining residue (RES; treated with HF/HCl; comparable with the humin fraction). The largest contribution to the total soil OM was found for EX and/or RES, the sum of which varied between 79% and 98% (Ave. 90.8%, n = 18). The minor contribution from the OLF (Ave. 4.4%) indicates that stabilisation within aggregates was not a major factor that contributed to OM stability in the studied profiles. Differences in molecular composition between the fractions were larger than those between profiles or with depth. The EX fraction showed the lowest contribution from plant (lignin phenols) and BC (PAHs, indenes, aromatics) derived products. The RES fraction showed a significantly larger contribution from BC related pyrolysis products compared to the EX. This non-extractable BC that is present in the RES after removal of the light fractions may reflect preferential binding of PAHs to minerals or, alternatively, the presence of highly condensed macromolecular polyaromatic structures. Changes with depth within the EX and RES fractions showed a larger contribution from products derived from BC in the anthropogenic horizons. Furthermore, the OM composition in EX and RES indicated that the degree of degradation of OM in anthropogenic horizons was relatively low. Apart from these similarities for anthropogenic horizons, the chemical composition of soil OM also showed large differences between both TPI soils. TPI-1 showed large variation between horizons while TPI-2 showed only minor changes with depth; this may be related to different phases of human occupation with time and/or a different soil usage.

To characterise soil humic acids (HAs) extracted from Spanish marshes formed under different vegetation types (Spartina maritima (GSp), Juncus maritimus (GJc), Phragmites australis (GPh), and Scirpus maritimus (VSc)), soil depths (0–20, 20–40 and 40–60 cm), physiographic position (low and high marshes), wetland types (salt marshes and lagoons) and environmental conditions (Atlantic and Mediterranean coast). Soil samples were collected in five Spanish marshes, three on the Galicia province and two on the Valencia province. Humic acids were extracted and their elemental composition, semiquinone-type free radical (SFR) content, FTIR and CPMAS 13C NMR spectra determined. Total carbon (TC), total nitrogen (TN), total sulphur (TS), CaCO3 content, and field pH and Eh (mV) in the marsh soils sampled were also measured. The field pH and Eh values were typical of coastal areas submitted to periodic inundations and the highest TC, TN and TS contents were found in the soil of lagoon marshes as an effect of physiographic position and wetland type. The HAs, in general, were highly aliphatic and exhibited a low SFR content, which suggests a low humification degree of the SOM formed in the studied areas. This is a result of the anaerobic decomposition to which SOM is submitted and the high input of plant-derived organic matter (OM) by vegetation. However, among the studied sites low salt marsh and subsurface layer of the high salt marsh showed higher SFR content, simpler FTIR spectra, higher lignin degradation and lower O-alkyl C/alkyl C ratio than the lagoon marshes, thus suggesting the presence of a more humificated SOM in these sites. From the different factors analysed, only physiographic position (low versus high salt marshes) and wetland type (marshes versus lagoons) caused variations in the HAs characteristics, because as the studied soils are under anaerobic conditions, they control the exportation of plant-derived OM and the allochthonous OM contribution in the studied areas.

This study on humic acids (HAs) of podzol horizons from the southeastern region of Brazil investigated the accumulation and degradation of soil organic matter (SOM) in warm-climate podzols. Humic acids from sandy coastal Spodosols (Histic Alaquod and Arenic Alorthod) from Cardoso Island in Sao Paulo State were characterized by pyrolysis in combination with gas chromatography and mass spectrometry (Py-GC/MS). The soils developed on quartziticsandynutrient-poor parent materials under restinga forest in a coastal area. The Py-GC/MS results show that the chemical composition of HAs in B horizons in one out of three profiles was influenced by both dissolved organic C (DOC) and C from in situ decaying roots. Carbon derived from DOC dominated in the deepest part of the B horizons. In the Arenic Alorthod (H9) profileSOM from the B horizon seemed to be largely derived from roots. The DOC-derived SOM was characterized by large contributions of phenolmethylphenolsand degraded polysaccharide productswhile root contributions were mainly characterized by lignin products. Aliphatics were most abundant in A horizons (E and EB horizons were not analyzed). Both DOC-derived and lignin-derived SOM showed distinct degradation patterns. The Py-GC/MS results corroborate those obtained by 13C variable amplitude cross polarization magic angle spinning nuclear magnetic resonance spectroscopy and Fourier-transform infrared spectroscopy. Molecular chemistry showed that podzol B horizons are variable in compositionand local influencessuch as drainage and vertical or lateral water transportand SOM decomposition play an important role in podzolization processes in warm climates.

We identified the effects of vegetation changes, and aerobic and anaerobic decay on the lignin composition in the Penido Vello peat record (Galicia, Spain). The ombrotrophic part of this peat record was dominated by graminoids and has significant contributions of ericoids at some depths. The organic matter (OM) of different peat fractions (bulk, NaOH-extractable fraction, and non-extractable residues) of 15 samples from the upper meter was analysed with pyrolysis-gas chromatography/mass spectrometry (pyrolysis-GC/MS). In addition, the dominant plant species were analysed, including Carex durieui, Agrostis curtisii, Molinia caerulea, Deschampsia flexuosa, Festuca rubra, Eriophorum angustifolium, Erica mackaiana and Calluna vulgaris, and their lignin composition compared to that of the peat OM. The high abundance of guaiacol and 4-formylguaiacol in fresh plant tissue compared to peat OM suggests that in addition to p-coumaric and ferulic acid (which are abundant in graminoids), other non-lignin phenolic monomers are contributed by graminoid species. For the non-lignin phenolics, graminoids differed from ericoids in the high abundance of ferulic acid (4-vinylguaiacol), while p-coumaric acid (4-vinylphenol) showed high and similar abundances in ericoids and graminoids. This result suggests that ratios between p-hydroxyphenyl (or p-coumaric acid) and other lignin moieties in (pyrolysates of) peat cannot be used as source indicator. Comparison of plant and peat fractions using factor analysis allowed a distinction between the effects of source (plant identity) and decay on the lignin composition of the Penido Vello peat, and different stages of decomposition were identified. Preferential decay of guaiacyl over syringyl moieties was found for the first stage of decay. This preferential decay is probably related to the large abundance of guaiacyl moieties in easily degradable non-lignin phenolics. Preferential decay of syringyl moieties occurred during subsequent aerobic decay.

Between 30 and 63% of the soil organic matter (SOM) is stored below 30 cm, making subsoil-SOM an important source and sink in the global carbon cycle. Nevertheless, detailed information on the composition of subsoil-SOM remains scarce. This study aims to evaluate the chemical composition of SOM in topsoil and subsoil horizons in broadleaved forests on acid loamy soils. Six sites were chosen in Northern Belgium under beech, oak and hybrid poplar, on Gleysols, Umbrisols, Cambisols and Albeluvisols on loamy Quaternary deposits. Analytical pyrolysis–gas chromatography/mass spectrometry (pyrolysis–GC/MS) was performed on the dialyzed alkaline extract, which represents between 41 and 90% of the total organic carbon for the selected sites. All extracts show a significant shift in chemical composition between the topsoil and the subsoil. While topsoil-SOM mainly differs according to input and nutrient status, subsoil-SOM shows high relative amounts of alkanes and alkenes or polysaccharides for coarse and fine textured soils respectively. Lignins, lignin-derived phenols or aromatics were not major contributors to subsoil-SOM, regardless of soil type. Furthermore, results show that very labile plant-derived molecules are present in the subsoil, i.e. long-chain aliphatics and (cellulose-derived) anhydrosugars. The organic matter signature of the subsoil samples was evaluated for typical indications of fresh material, decay, podzolisation and anaerobic processes, and indicates root input and stabilization of certain labile plant-derived compounds against microbial decay to be important in the subsoil.

Soil organic matter (SOM) in Alu-andic Andosols and Alu-humic Umbrisols is believed to accumulate because of the protection caused by binding to aluminium (Al). We investigated soils that differed in the abundance of organo-Al complexes to determine the effect of such binding on SOM chemistry. For this, the surface horizons of three types of acid soils in the Basque Country (northern Spain) under forest stands were studied: (i) Alu-andic Andosols (AND soils) on basalts and trachytes, (ii) Umbrisols or so-called 'aluminic'(ALU) soils also on basalts and trachytes and (iii) soils with a podzolizing trend (POD), on quartzites. Values of Al extractable with sodium pyrophosphate (Alp) in the surface horizons of these soils ranged between 8.5 and 13.1, 1.9 and 9.3, and 0.8 and 3.7 g kg-1 dry weight, for the AND, ALU and POD soils respectively. For POD and ALU soils, surface horizons were sampled at two depths, 0-5 and 5-20 cm, whereas the AND soils were sampled at different depths down to the B horizon. NaOH-extractable SOM from three AND soils, 12 ALU soils and 12 POD soils was studied by pyrolysis-gas chromatography/mass spectrometry. The POD soils had the largest loads of plant-derived markers (lignin, long-chain alkanes and alkenes, methyl ketones, fatty acids); SOM of the AND soils had the smallest amounts of plant-derived SOM and the largest amounts of microbial products (microbial sugars and N-compounds) of the soils studied. ALU soils had an intermediate pattern, as expected. The results indicate that the SOM of Alu-andic Andosols, developed from basalt and trachyte rocks, is essentially dissimilar to that of soils derived from quartz-rich parent material, under the same climate conditions and similar forest stands. The dominance of secondary (microbial-derived) SOM in Alu-andic Andosols, also observed in previous research on Sil-andic Andosols (these are dominated by short-range ordered Si compounds in contrast to the dominance of organo-Al complexes in Alu-andic Andosols), reveals the small contribution of primary (plant-derived) material to SOM in soils with andic properties. © 2011 The Authors. Journal compilation © 2011 British Society of Soil Science., M.S.A.’s period at Wageningen University was funded by INIA, Instituto Nacional de Investigación y Tecnología Agraria y Alimentación (proyecto SUM2006-0013.00.00). N.G.B. was funded by the same Project.

n-Alkane distributions are frequently used as palaeoclimate proxies in ombrotrophic peat deposits. Although n-alkane distributions differ strongly between plant species, n-alkanes are not species-specific molecules. For a proper interpretation, it is important to understand the different abundances of n-alkanes in various plant species as well as the changes that occur when plant litter is transformed to peat. In particular because molecular markers are especially valuable in highly decomposed peat where plant remains are no longer recognizable, it is important to understand the effects of decomposition on n-alkane distributions. The organic matter (OM) of a high-resolution sampled, 9 m thick, ombrotrophic peat deposit from Tierra del Fuego was analysed with pyrolysis-gas chromatography/mass spectrometry (pyrolysis-GC/MS). The same samples were analysed for carbon (C) and nitrogen (N) content. Depth profiles of C:N ratio, the summed lignin and summed polysaccharide pyrolysis products, and markers specific for Sphagnum spp., Empetrum rubrum and Nothofagus antarctica, enabled a reconstruction of changes in vegetation composition to be made. This reconstruction was used to examine the validity of the n-C23 alkane to indicate Sphagnum and the summed long chain n-alkanes (C29 and C31) to reflect leaf input of the woody species E. rubrum and N. antarctica. Our results show that even in Sphagnum-dominated peat, the n-alkane distribution is not determined by Sphagnum but by leaf input of E. rubrum and N. antarctica. However, good correlations between the n-C23 alkane and the Sphagnum marker 4-isopropenylphenol, and between the summed n-C29 and n-C31 alkanes and the marker of N. antarctica support that their relative change with depth can be used to indicate the abundance of these species in Sphagnum-dominated peat. In peat with relatively low contributions of Sphagnum, both n-alkane proxies (C23 and C29 + C31) reflect the degree of decomposition. We evaluated the influence of Sphagnum dominance, decomposition, and pyrolysis on the n-alkane distributions in peat OM.

While the influence of climate, vegetation, management and abiotic site factors on total carbon budgets and turn-over is intensively assessed, the influences of these ecosystem properties on the chemical complexity of soil organic matter (SOM) remains poorly understood. This study addresses the chemical composition of NaOH-extracted SOM from maritime temperate forest sites in Flanders (Belgium) by pyrolysis-GC/MS. The studied forests were chosen based on dominant tree species (Pinus sylvestris, Fagus sylvatica, Quercus robur and Populus spp.), soil texture and soil-moisture conditions. Differences in extractable-SOM pyrolysis products were correlated to site variables including dominant tree species, management of the woody biomass, site history, soil properties, total carbon stocks and indicators for microbial activity. Despite of a typical high intercorrelation between these site variables, the influence of the dominant tree species is prominent. The extractable-SOM composition is strongly correlated to litter quality and available nutrients. In nutrient-poor forests with low litter quality, the decomposition of relatively recalcitrant compounds (i.e. short and mid-chain alkanes/alkenes and aromatic compounds) appears hampered, causing a relative accumulation of these compounds in the soil. However, if substrate quality is favorable, no accumulations of recalcitrant compounds were observed, not even under high soil-moisture conditions. Former heathland vegetation still had a profound influence on extractable-SOM chemistry of young pine forests after a minimum of 60 years.

Humic acids have been widely investigated by spectroscopic methods, especially NMR and FTIR, and they are known to show significant differences according to their origin. Low resolution methods such as NMR and FTIR, however cannot easily distinguish different input sources or establish relations between SOM chemistry and vegetation or land use in general. High resolution methods, such as analytical pyrolysis and pyrolysis combined with methylation do offer such possibilities. Therefore, HAs from five reference soils called the Eurosoils, including a Vertic Cambisol (E1, Italy), a Rendzina (E2, Greece), a Dystic Cambisol (E3, Great Britain), an Orthic Luvisol (E4, France) and an Orthic Podzol (E5, Germany), that were previously characterized a.o. by NMR, FTIR and ESR, were also analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and thermally assisted hydrolysis and methylation (THM) and subsequent analysis by GC/MS. The Orthic Podzol sample showed the largest aliphaticity, and the strongest degradation of aliphatics and lignin. The Dystric Cambisol featured the least decomposed HA, which was reflected by a large content of long-chain alkanes, and little lignin degradation. Both the Dystric Cambisol and the Orthic Luvisol HAs contained a significant amount of microbial organic matter. Polyaromatics, which indicate the presence of charred material, were most abundant in the Vertic Cambisol and the Podzol HAs and lowest in the Dystric Cambisol and the Rendzina HAs. THM was able to distinguish between the various vegetations/land uses. Although quantifications by NMR and py-GC/MS are essentially different, the general results largely coincided. NMR appears to underestimate aromaticity and overestimate aliphaticity, but a molecular mixing model yielded reasonable correlations between NMR and pyrolysis data. Classification by ‘degradation state’ based on py-GC/MS largely coincided with acidity determined by titration, but FTIR data did not coincide. Py-GC/MS, with its much larger resolution, is a better tool to distinguish effects of vegetation, microbial input, and degradation. HA's produce the same variety of compounds upon pyrolysis as total SOM extracts and are therefore chemically not more simple than SOM. HA chemistry, however can be understood in the light of land use history and SOM dynamics.

The effect of elevatedCO2and nitrogen fertilization on the molecular chemistry of litter of threePopulusspecies and associated soil organic matter (SOM) was investigated by pyrolysis-gas chromatography/mass spectrometry. The results are based on 147 quantified organic compounds in 24 litter samples. Litter ofP. euramericawas clearly different from that ofP. nigraandP. alba. The latter two had higher contents of proteins, polysaccharides, and cutin/cutan, while the former had higher contents of phenols and benzofurans/pyrans. The difference between replications was at least as large as the effect of treatments, so that no systematic chemical changes were attributable toCO2effect or N-fertilization effect. The chemistry of SOM under the various species and treatments did not show significant changes either. The low number of available replicates that is two was clearly insufficient to overcome the effect of spatial variation on litter chemistry and detect small differences in molecular litter chemistry.

Soil organic matter (SOM) is a key factor in ecosystem dynamics. A better understanding of the global relationship between environmental characteristics, ecosystems and SOM chemistry is vital in order to assess its specific influence on carbon cycles. This study compared the composition of extracted SOM in 18 topsoil samples taken under tundra, taiga, steppe, temperate forest and tropical forest using pyrolysis–GC/MS. Results indicate that SOM from cold climates (tundra, taiga) still resembles the composition of litter, evidenced by high quantities of levosugars and long alkanes relative to N-compounds and a clear odd-over-even dominance of the longer alkanes. Under temperate conditions, increased microbial degradation generally results in a more altered SOM chemistry. SOM formed under temperate coniferous forests shows an accumulation of aromatic and aliphatic moieties, probably induced by substrate limitations. Tropical SOM was characterized by an SOM composition rich in N-compounds and low in lignins, without any accumulation of recalcitrant fractions (i.e. aliphatic and aromatic compounds). Lignin composition moreover varies according to vegetation type. Results were validated against 13 new samples. The humic signature of topsoil organic matter formed under different biomes indicates a dominating effect of (i) SOM input composition related to vegetation, and (ii) SOM breakdown reflecting both climate and input quality. No evidence was found for a chemically stabilized SOM fraction under favorable decomposition conditions (temperate or warm climate with broadleaved vegetation).

Soil organic matter in a chronosequence of Michigan soils (Spodic Udipsamments and precursors) was studied in thin section and by pyrolysis-gas chromatography/mass spectrometry (GC/MS). The Michigan soils were compared with a well-drained Dutch Typic Haplorthod that was studied with the same methods. Both techniques indicate that most B-horizon organic matter in the Michigan sequence is root- and char-derived and not due to illuviation. Microbial matter contributes significantly to B-horizon chemistry. Although charcoal is common in A horizons, it hardly contributes to soil organic matter (SOM) chemistry in this horizon, while it constitutes a significant part of B-horizon C. This suggests that silt-size particulate charcoal is transported downward. Nitrogen-containing pyrolysis fragments are abundant, which, together with significant amounts of aromatic components, points to contribution of proteins. The Michigan soils are far less rich in alkyl C than the Dutch counterpart. This suggests a much lower residual accumulation of recalcitrant compounds in the former, probably due to a larger contribution of root litter and a more efficient decomposition. Faster decomposition (shorter mean residence time) in the Michigan soils is also suggested by the low accumulation of SOM in the B horizon. Thus we can conclude that in the Michigan soils, dissolved organic matter contributes significantly to transport of Al and Fe, but essentially without illuviation of organic matter in the B. In the Dutch Spodosol, on the other hand, both transport of dissolved organic C to the B horizon and accumulation of SOM through decomposition of roots play important roles. Pyrolysis-GC/MS is a powerful tool in deciphering organic-matter-related aspects of soil genesis. The formation of many soils is organic matter driven, and this aspect is still poorly understood.

The soil memory recorded in paleosols of loess-paleosol sequences is an important contributor to our understanding of past climatic conditions. Molecular proxies based on the organic matter preserved in paleosols form an essential part of this record, but the long-term preservation of SOM is poorly understood, especially for sediment traps and slope profiles. This paper addresses the composition of organic material from the Early Weichselian A-horizons of the Rocourt paleosol, a major paleostratigraphic marker for the Eemian and Early Weichselian in Western Europe. NaOH-extractable organic matter from an exceptionally thick Rocourt profile in the Kesselt Quarry (Belgian Loess Belt) was analyzed by pyrolysis-Gas Chromatography/Mass Spectrometry (pyrolysis-GC/MS) and the results evaluated against paleopedological data. The molecular composition of the organic matter at Kesselt was compared with reference samples from two nearby quarries (including the type locality at Veldwezelt-Hezerwater), and to a sample from the contemporary Nussloch sequence in Germany. The SOM composition found at the four sites indicated a large content of microbial matter and was dominated by carbohydrates and N compounds, many of which were not reported before from SOM pyrolysates. Differences in the molecular composition between samples, both within profiles and between sites, coincided with differences in landscape position (slope-shoulder-plateau) and fossil redox conditions (surface gleys). Samples form drier and more upland situations contained more burnt material, while samples from slope profiles and surface gleys contained even more microbial material, in particular chitin. Results therefore suggest that the admixture of microbial SOM is considerable in loess-paleosols and that differences in edaphic conditions (in particular slope position and soil moisture) and occurrence of wildfires are important for the long-term preservation of SOM. These should therefore be considered when interpreting biogeochemical proxies.

We performed solid state 13C cross-polarization magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy and pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) on the Penido Vello peat deposit located in Galicia, NW Spain. Often regarded as complementary techniques, solid state 13C NMR and Py–GC/MS are widely used for the characterisation of organic matter. Recently, a molecular mixing model (MMM) was proposed to predict the distribution of C in biochemical components (carbohydrate, protein, lignin, lipid, char) from the 13C NMR spectral distribution, thereby allowing a quantitative comparison with Py–GC/MS product abundances. We discuss the application of this model to a peat core, by comparing NMR-MMM results with Py–GC/MS data. The core represents ∼5000 yr accumulation and ranges from fibric (at the surface) to hemic (bottom). The amounts of carbohydrates and lipids predicted by the MMM and calculated from the quantified Py–GC/MS chromatograms are in close agreement. However, the well known low capability of the conventional Py–GC/MS method to provide structural information on proteins from bulk soils, the poor GC amenability of polar compounds and many other possible sources of inaccuracy in Py–GC/MS and NMR-MMM caused discrepancies with predictions made with the MMM. Also, the MMM failed to give good prediction of the C/N ratio of the peat material. Although the NMR-MMM approach does not account for molecular transitions during decomposition, this oversimplification proved to be acceptable. The MMM seems to be a useful tool for the interpretation of NMR spectral distributions in peat material.

Kauri is known to cause low soil pH and loss of Al from the Al-hydroxy-interlayers from interlayered vermiculite. Kauri is also associated with intense podzolisation and therefore we studied the Al and Fe phases in soil under kauri and under adjacent broadleaf/treefern vegetation for comparison. Kauri accumulates significantly higher amounts of organic matter, which cause a significantly lower soil pH. This lower soil pH under kauri results in increased breakdown of alumino-silicates relative to broadleaf/treefern vegetation. At the same time, the larger amount of organic carbon in soils under kauri causes higher amounts of bound Al and Fe. In Ah-horizons under kauri, sesquioxides appear to be protected by organic matter, which renders them inaccessible to oxalate extraction. The distribution of pyrophosphate-extractable Fe and Al suggests podzolisation, but is due to a combination of transport and local weathering and complexation. The effect of kauri on the soil, as compared to adjacent tree species, appears to be generated by its longevity: large amounts of litter and leachates on one site, rather than its litter quality.

The net accumulation of remains of Sphagnum spp. is fundamental to the development of many peatlands. The effect of polyphenols from Sphagnum on decomposition processes is frequently cited but has barely been studied. The central area of the Rodmossamyran peatland (Sweden) is an open lawn that consists mostly of Sphagnum spp. with a very low contribution from vascular plants. In order to determine the effects of decay on sphagnum phenols, 53 samples of a 2.7 m deep core from this lawn were analysed with pyrolysis gas chromatography–mass spectrometry (pyrolysis-GC–MS) and compared with more traditional decomposition proxies such as C/N ratio, UV light transmission of alkaline peat extracts, and bulk density. Factor analysis of 72 quantified pyrolysis products suggested that the variation in 4-isopropenylphenol was largely determined by aerobic decomposition instead of Sphagnum abundance. In order to evaluate the effects of aerobic decay in Sphagnum peat, down-core records from different climatic regions were compared using molecular markers for plant biopolymers and C/N ratio. These included markers for lignin from vascular plants ((di)methoxyphenols), polyphenols from Sphagnum spp. (4-isopropenylphenol), and cellulose (levoglucosan). Our results indicate that polyphenols from Sphagnum are preferentially degraded over polysaccharides; consequently the variability of the marker for sphagnum acid, 4-isopropenylphenol, was found indicative of decomposition instead of reflecting the abundance of Sphagnum remains. The fact that 4-isopropenylphenol is aerobically degraded in combination with its specificity for Sphagnum spp. makes it a consistent indicator of past hydrological conditions in Sphagnum-dominated peat. In contrast, the variability of C/N records in Sphagnum-dominated peat was influenced by both vegetation shifts and decomposition, and the dominant effect differed between the studied peatlands. Our results provide direction for modelling studies that try to predict possible feedback mechanisms between peatlands and future climate change, and indicate that the focus in Sphagnum decay studies should be on carbohydrates rather than on phenolic compounds.

Changes in soil organic carbon (SOC) contents with soil cultivation have been investigated extensively, but information on the influence of land use changes on the chemistry of soil organic matter (SOM) and SOM fractions is scarce. To make a contribution in this context, we sampled silty soils under different land use (spruce forest (Ah horizon, 0–7 cm), continuous maize cropping (Ap horizon, 0–30 cm), and grassland (Ah horizon, 0–10 cm)) as well as the organic layer (L, Of, and Oh) of the forest floor and collected plant materials from the three sites. Separation of SOM density fractions (free particulate organic matter, occluded particulate organic matter, and mineral-associated organic matter) and water-stable aggregate size fractions of the surface soils was performed in order to follow changes in the chemical composition of SOM in physical soil fractions using CPMAS 13C NMR spectroscopy and to determine land use effects on the chemistry of SOM fractions. The CPMAS 13C NMR spectra showed that maize litter had the highest content of O-alkyl-C and the lowest content of alkyl-C, aryl-C and carbonyl-C compared with the plant material from the spruce stand and the grassland. The forest litter had the largest content of aromatic and alkyl-C. Decomposition of spruce litter in the humus layer resulted in a decreasing O-alkyl-C content and an increasing alkyl-C content. The SOM of the acid forest soil consisted mainly of particulate organic matter (POM) with a high content of spruce litter-derived alkyl-C. The SOC stocks in the grassland and maize soil were dominated by mineral-associated SOM which contained relatively larger proportions of aryl and carbonyl-C. The decrease of the SOC concentration induced by cultivation resulted in a relative accumulation of aromatic C structures in the mineral-bound SOM. In all soils, the free POM had a smaller proportion of alkyl-C and a larger proportion of O-alkyl-C than the POM occluded in aggregates. The mean age of the SOM in the density fractions of the maize soil increased with increasing aromaticity in the order free POM

Present models of podzolisation emphasize the mobilization and precipitation of dissolved organic matter. together with Al(-silicates) and Fe. Such models cannot explain the dominance of pellet-like organic matter in most boreal podzols and in well-drained podzols outside the boreal zone, and the discrepancy between the chemistry of percolating organic matter (DOC) and the organic matter accumulated in well-drained podzol-B horizons. The present paper offers an amended podzolisation theory, in which relative contribution of illuviated organic matter and root litter together with organic matter dynamics provide an explanation for the large variation in podzol morphology, It is suggested that fast organic matter dynamics as occurs on nutrient-rich parent materials in the boreal zone causes small accumulation of organic matter, mainly derived from roots. In such soils. the colors of Fe components dominate in the B horizon. Slow organic matter dynamics, as occurs on nutrient-poor parent materials and under hydromorphic circumstances, favors large organic matter accumulations in the B horizon. and a larger abundance of DOC-derived organic matter coatings. The latter group includes tropical podzols. (C) 2004 Elsevier B.V. All rights reserved.

A well-developed podzol hydrosequence that has been partially covered with drift sand, and partially subjected to improved drainage, provides new insights into the causes of variation in soil organic matter chemistry in such soils. While E horizons invariably move towards a dominance of aliphatic components reflecting residual accumulation, the chemistry of organic matter in well-drained B horizons is determined mainly by decaying roots, which are transformed by microorganisms to humus aggregates. In poorly drained, stratified B horizons, humus coatings dominate and the chemistry is very close to that of dissolved organic carbon. When a sand cover inhibits the supply of fresh litter, microbial decomposition in the A horizon causes a shift in chemistry towards that of the E horizon. Similarly, upon improved drainage and removal of complexed metals from the top of the B horizon, microbial decomposition of all palatable organic matter in the top of the B horizon causes a shift towards E-horizon chemistry. This is probably the mechanism by which most E horizons in podzols are formed, and not by re-solution. Marked chemical changes upon improved drainage may take only decades. During microbial decay, small polysaccharide-derived pyrolysis products (mainly furans, furaldehydes and acetic acid) remain abundant due to the contribution of microbial sugars. Both micromorphology and factor analysis on quantified results of pyrolysis-gas chromatography/mass spectrometry contribute significantly to the interpretation of the humus chemistry of these profiles and thus to our understanding of soil genesis. Organic chemistry of the investigated podzols can be understood only in the context of their genesis

We hypothesised that, during occlusion inside granular aggregates of oxide-rich soils, the light fraction organic matter would undergo a strong process of decomposition, either due to the slow process of aggregate formation and stabilisation or due to digestion in the macro- and meso-fauna guts. This process would favour the accumulation of recalcitrant materials inside aggregates. The aim of this study was to compare the dynamics and the chemical composition of free and occluded light fraction organic matter in a natural cerrado vegetation (woodland savannah) and a nearby pasture (Brachiaria spp.) to elucidate the transformations during occlusion of light fraction in aggregates of a clayey Oxisol. Nuclear Magnetic Resonance of the 13C, with Cross Polarisation and Magic Angle Spinning (13C-CPMAS-NMR), and 13C/12C isotopic ratio were combined to study organic matter composition and changes in carbon dynamics, respectively. The occluded light fraction had a slower turnover than the free light fraction and the heavy fraction. Organic matter in the occluded fraction also showed a higher degree of decomposition. The results confirm that processes of soil organic matter occlusion in the typical "very fine strong granular" structure of the studied oxide-rich soil led to an intense transformation, selectively preserving stable organic matter. The small amount of organic material stored as occluded light faction, as well as its stability, suggests that this is not an important or manageable sink for sequestration of atmospheric CO2. O presente estudo tomou, como referência, a hipótese de que, durante a oclusão dentro de agregados granulares de solos ricos em óxidos, a fração leve da matéria orgânica do solo passa por um intenso processo de decomposição, decorrente do lento processo de formação desses agregados ou da digestão no trato digestivo da meso e macrofauna. O objetivo deste trabalho foi comparar a dinâmica e a composição química das frações leves (livre e oclusa)s de um solo sob vegetação de cerrado e uma pastagem (Brachiaria spp.) adjacente, para elucidar as transformações durante o processo de oclusão da fração leve em agregados de um Oxissol argiloso. As técnicas de Ressonância Magnética Nuclear do 13C, com Polarização Cruzada e Ângulo Mágico de Rotação (13C-RMN-PCAMR), e de análise da relação isotópica 13C/12C para acessar, respectivamente, a composição e dinâmica dos materiais orgânicos presentes. A fração leve oclusa apresentou um tempo de ciclagem bem maior, quando comparada à fração leve livre e a pesada. A matéria orgânica nessa fração também apresentou maior grau de decomposição. Segundo os resultados, o processo de oclusão de matéria orgânica nas típicas estruturas "granulares fortes muito pequenas" dos solos ricos em óxidos levou esse material a sofrer uma intensa transformação, preservando seletivamente matéria orgânica estável. As pequenas quantidades de carbono acumuladas na fração leve oclusa, assim como sua estabilidade, indicaram não representar essa fração importante e manejável sumidouro de CO2 atmosférico.

Sedimentary stratification identified by field descriptions of 12 soils derived wholly or partly from volcanic materials was compared with results obtained by chemical analyses (contents and ratios of lithogenic elements, contents of heavy metals) and detailed grain-size data after removal of organic matter and amorphous fractions. The finest sedimentary stratification was indicated by cluster analysis of ratios of lithogenic elements and by the grain-size analyses. Sedimentary stratification in the field is difficult to determine or describe when (1) the deposits are strongly weathered, (2) soil horizon boundaries coincide with stratification boundaries or (3) stratification is very fine. Nevertheless, field descriptions are a reasonably good way of differentiating parent materials, though they often underestimate the number of sedimentary layers. (C) 2003 Elsevier B.V. All rights reserved.

To gain understanding about the process of global warming, it is essential to study the global C cycle. In the global C cycle, soil organic matter (SOM) is a major source and sink of atmospheric C. Turnover times of C in these soil organic compounds vary from hours to thousands of years. Clay minerals can stabilize SOM through the formation of organo-mineral bonds. The aim of this research was first, to determine the mean residence time (MRT) of organic matter that is bound to different clay mineral surfaces, and second, to explain the variance in the measured MRTs using multilinear regression. We especially studied organic matter that is bound to kaolinite or smectite. We analyzed the 14C activity of organic matter in the whole and heavy clay-size fraction of kaolinite- and smectite-dominated soils from N'Ropa, in northern Mozambique. The soils originated from natural savanna systems and bamboo forest. We assumed that C inputs and outputs are in equilibrium in such soils, so that the 14C age equals the MRT of the organic C. For both kaolinite- and smectite-dominated soils, the organic matter in the whole and heavy clay-size fraction and extracts had a fast turnover (400?500 yr on average). The MRT of kaolinite-bound organic matter did not differ significantly from that of smectite-bound organic matter. Multiple linear regression indicates that the effective cation-exchange capacity (ECEC) is the main factor to explain variance in the MRT of the extracted SOM. These results agree with previously found trends in organic matter turnover of kaolinite and smectite-associated clay.

To gain insight into the effect of clay mineralogy on the turnover of organic matter, we analysed the C-14 activity of soil organic matter associated with clay in soils dominated by kaolinite and smectite in natural savanna systems in seven countries. Assuming that carbon inputs and outputs are in equilibrium in such soils, we took the C-14 age as mean residence time of the organic matter. We corrected the C-14 activity for the Suess effect, Bomb effect and difference between date of sampling and date of C-14 measurement. Organic matter associated with kaolinite turned over fast (360 years on average). Organic matter associated with smectite turned over relatively slowly, with an average mean residence time for the whole clay-size fraction of 1100 years. Multiple linear regression indicates that clay mineralogy is the main factor explaining differences in the mean residence time of the organic matter extracted.

Reclamation of Brazilian cerrados (savannas) has been intensified in the last decades, with implications for soil quality and soil organic matter (SOM) dynamics. Studying the impact of different tillage systems is essential to define better strategies for land use in Cerrado, which may favor C sequestration and improve soil quality. We used density fractionation and C-13 natural abundance to assess changes in SOM in an Oxisol previously under a cerrado sensu-stricto following 30 years of cultivation. The objectives of the study were to: (i) evaluate the long-term impact of tillage systems on SOM stocks in a Dark Red Latosol (Oxisol) from the Cerrado Biome, and (ii) better understand the dynamics of SOM in different density fractions of this soil. Cultivation led to compaction, which significantly increased soil bulk density. This resulted in the systematic overestimation of C and N stocks in cultivated areas when compared to the natural cerrado. Conversion of the cerrado into cropland using plow tillage (PT) or no-tillage (NT) system did not alter the total C (similar to100 Mg ha(-1)) and N (similar to7 Mg ha(-1)) stocks in the first 45 cm depth at the end of 30 years of cultivation. However, about 22% of the total C was replaced by C from maize. The relative replacement of C decreased following the order: free light fraction (F-LF) > heavy fraction (HF) > occluded light fraction (O-LF). The low substitution in the O-LF was attributed to a possible presence of charcoal. Converting cerrado into cropland significantly decreased F-LF quantity. The proportions of C replacement in this fraction were higher in PT than NT, suggesting a faster turnover in PT. Nevertheless, because most C (similar to95%) was held in the HF, C dynamics in the whole soil were controlled by the behavior of this fraction. The maintenance of C levels even at the end of 30 years of cultivation and the lack of differentiation between NT and PT were attributed to the high clay contents and Fe + Al oxi-hydroxides concentrations of the studied soil as well as to a sufficient C supply by the maize crop. (C) 2003 Elsevier Science B.V. All rights reserved.

Most knowledge about the degradation of lignocellulose in natural environments is based on woody tissue and aerobic systems; however, in peatlands the contribution of graminoids to organic matter (OM) is often significant and anaerobic conditions prevail. In order to reconstruct past environmental conditions from peatlands and predict possible feedback mechanism between peatlands and climate change, a better understanding of the decomposition of graminoid tissue and the effects of anaerobic conditions on decomposition are needed. Samples (51) from the upper 1 m of the graminoid-dominated Penido Vello peatland (Xistral Mountains, Galicia, NW Spain) were analysed with pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) and 13C cross polarisation magic angle spinning nuclear magnetic resonance spectroscopy (13C CPMAS NMR). Carbon and nitrogen contents were also determined. Depth profiles of molecular groups identified using 13C CPMAS NMR were consistent with those of depth-related distributions of quantified pyrolysis products (aliphatics, polysaccharides and aromatics). Molecular proxies were selected from peat pyrolysates to reflect the state of decay of 1) lignocellulose (the summed lignin and polysaccharide pyrolysis products, Lg and Ps, respectively), 2) lignified cellulose (levoglucosan/Ps) and hemicellulose (4-hydroxy-5,6-dihydro-(2H)-pyran-2-one/Ps), 3) macromolecular lignin including syringyl (S), guaiacyl (G) and p-hydroxyphenyl (H) ratios (S/G; H/(S + G), and side chain oxidation and shortening (vanillic acid/G, syringic acid/S, 4-acetylguaiacol/G, 4-acetylsyringol/S, C3-guaicols/G and C3-syringols/S) and 4) non-lignin phenolic acids (4-vinylphenol/H, 4-vinylguaiacol/G). Factor analysis was applied to these proxies and 120 quantified pyrolysis products to examine the influence of possible underlying factors that could explain the observed variation. Botanical changes and several degradation stages including surface decay (both aerobic and anaerobic), aerobic sub-surface decay and depth related decay (long-term anaerobic) were identified with factor analysis and all affected the variance of lignin-based decomposition proxies. The net effect of these environmental factors on the lignin proxies was examined using their depth records. This revealed that some lignin decomposition proxies were not in agreement with the literature: 1) G and S moieties with a C3 alkyl side chain showed no correlation with bog hydrology at the time of peat formation; 2) G and S moieties with acetyl side chains were related to both relatively dry (secondary aerobic decay) and wet (first stage of decay) conditions; 3) vanillic acid and syringic acid were related partly to ericoids (indicating dry conditions) and partly to free phenolic acids (less depleted under wet conditions); and 4) preferential decay of G over S moieties was found during the first stage of decay (both aerobic and anaerobic) and long-term anaerobic decay. These contradictions can be explained by the dominance of non-woody lignin sources (graminoids) and the prominence of anaerobic decay in peatlands. Our findings indicate that the effect of anaerobic decay and source vegetation should be considered when using lignin proxies to deduce aerobic decay in peat records.

The stability to thermal oxidation of soil humic extracts saturated with H, Na, Ca, or Al, was followed after treatment with relatively polar organic compounds, such as methanol, formic acid, and acetic acid. While thermal characteristics of H-humates did not change upon addition of the polar molecules, thermal decomposition (oxidation) of Na-humates was shifted to much higher temperatures (750–830 � C) than control. Substantially less dramatic was the effect on Ca-humates, whereas hardly any alteration was observed when polar organic compounds were added to Alhumates. These results can be explained by considering the forces that hold humic molecules together. Humic components are strongly bound to each other by hydrogen bonding in H-humates and by electrostatic bridges in Ca- and Alhumates. These binding forces were not overcome by the simple addition of polar organic molecules, and their stability remained generally unchanged. In Na-humates, associations of humic molecules are held together only by non-specific hydrophobic interactions. Our results showed that wetting the relatively more flexible Na-humates with organic solvents slightly less polar than water caused a significant increase in thermal stability. Because most polysaccharide-C has largely disappeared at 400 � C, this thermal behaviour can be explained by the rearrangement of largely hydrophobic humic components in methanol, leading to an increase in association energy. The intensity and reversibility of thermal stabilization indicate that association occurred among relatively small molecules rather than among macromolecules. Also Na-saturated humus of bulk samples showed an increase in stability against oxidation upon addition of methanol. These findings suggest that, counter-ions and amphiphilic organic compounds may affect organic matter stability also in natural soils. # 2002 Elsevier Science Ltd. All rights reserved.

Cross-polarized magic-angle-spinning NMR (CPMAS-NMR) techniques are assumed to be only semi-quantitative in the assessment of carbon distribution in humic substances or natural organic matter, due to a number of interferences such as spinning side bands (SSB) in spectra, paramagnetic species in samples, and low or remote protonation of aromatic carbons. Fast rotor spin rates or direct polarization NMR techniques are normally applied to improve quantitative signal detectability. Variable contact time pulse sequences were used here to obtain CPMAS-NMR spectra of organic compounds of known structure and different humic substances. Integration of spectral areas, previously subtracted of SSB, and relative stoichiometric factors were used for mathematical elaboration to calculate the elemental content in samples. These values did not significantly differ from those obtained by direct determination of elemental content with quantitative elemental analysis. Our results showed that the carbon observed CPMAS-NMR provides a quantitative representation of the whole carbon content in humic substances.

Preparative high performance size exclusion chromatography (HPSEC) was used to size-fractionate a humic acid (HA) solution with 0.05 M ionic strength before and after having made the humic solution 0.5 x 10(-3) M in acetic acid (AcOH). Size-fractions were characterized by pyrolysis-gas-chromatography/mass spectrometry (Pyr-GC-MS) and 1H NMR spectroscopy. Pyr-GC-MS showed that the AcOH treatment altered the distribution of humic molecular components in the size-fractions. The unsaturated alkyl chains were moved from size-fractions of larger molecular-size into those of lower molecular-sizes. Most of the aromatic moieties, which were found in larger molecular-size fractions for the untreated HA, were spread into fractions of lower molecular size after AcOH addition to HA. Carbohydrates, which were undetectable in anyfraction of the untreated HA, appeared instead in the pyrogram of the lowest molecular-size and most hydrophilic fraction after treatment with AcOH. Our results suggested that AcOH disrupted the weakly bound association of humic supramolecularstructures and HPSEC elution separated size-fractions of different composition without losing humic matter by adsorption on the HPSEC column. The fractions with the largest apparent molecular size were the richest in alkyl chains, thereby suggesting that humic molecules were stabilized into supramolecular associations by multiple weak interactions among apolar groups such as alkyl chains and aromatic moieties. 1H NMR spectra of size-fractions were greatly simplified and more resolved after AcOH treatment. This was attributed to a less complex molecular association in the size separates which provided a larger solubility in the NMR solvent and more favorable relaxation times. Combination of the procedure used here for size-fractionation with NMR and Pyr-GC-MS methods appears to be promising to advance knowledge on the molecular composition of humic substances.

In order to better understand the dynamics of soil organic matter (SOM) in Oxisols and the impact of converting native cerrado (savannah) into pasture, we studied the dynamics of different physically separated SOM pools at different depths in a cerrado oxisol (Typic Haplustox), under natural conditions and after 23 years of cultivated pasture (Brachiaria spp.) via the replacement of the native C (C3-derived) by pasture C (C4-derived). Organic C stocks of the original cerrado (15±3 kg m−2) and pasture (17±3 kg m−2) were not significantly different, which was attributed to the high biomass production of the tropical grasses and the protective effect of the high clay content (>800 g kg−2). We observed that 89–91% of the total organic C accumulated in the clay+silt fraction. The replacement of cerrado-derived C by pasture-derived C was in average 36%, 34%, and 19% for Ap, AB1, and Bw2 horizons, respectively, suggesting a fast turnover rate of organic C regardless of the high clay content. The replacement decreased in the order: free low-density organic matter (LDOM)>heavy fractions (sand, silt, clay)>occluded-LDOM. The lower replacement of the occluded-LDOM compared to the heavy fractions was attributed to protection inside aggregates and to a possible accumulation of C3-derived charcoal (black carbon). After 23 years of pasture, about 50% of the total organic C in the free-LDOM in the topsoil was still from cerrado, indicating that a significant part of this fraction was relatively recalcitrant. Charcoal fragments observed in the fraction suggested that the recalcitrance was probably due to charred material.

Differences in soil organic matter (SOM) composition in consecutive soil profiles (under algae, grass, moss, heather and pine) from a primary vegetation succession (central Netherlands) were investigated by Cross Polarization-Magic Angle Spinning (CPMAS) 13C NMR, chemical degradation (acid hydrolysis of polysaccharides) and pyrolysis-GC/MS (Py-GC/MS) in relation to the vegetation. All mineral soil horizons had lower contents of polysaccharides than the ectorganic layer and/or the fresh plant material as suggested by the diminishing O-alkyl peaks by NMR. The monosaccharide distribution pointed to an increase of microbial sugars in the soil as suggested by the raising C6/C5 ratios. Soil polysaccharides may be accompanied by a significant contribution of carbohydrates from mosses in the first stages, because the undecomposed moss tissues have high C6/C5 ratios, which falsify the usual interpretation that such high ratios may be due to microbial sugars. Fresh litter and ectorganic layers under heather and pine had similar contents of aromatics, but the contribution of lignin (guaiacols and syringols) was lower in the ectorganic horizons. The degree of oxidation, as determined by the acid/aldehyde ratio, increased with progressive humification. All Ah horizons contained less aromatics, more oxidized lignin remnants and higher amounts of aliphatic compounds than the litter. One or two macromolecules, which produced n-alkenes/n-alkanes and branched alkenes/alkanes upon pyrolysis and were derived from mosses, were mainly responsible for the accumulation of aliphatics in soil, although other aliphatic polymers, such as suberin, might also play an important role. Preservation of components from earlier vegetation might significantly influence SOM composition.

Summary Ultrasonic energy has been widely used to disrupt soil aggregates before fractionating soil physically when studying soil organic matter (SOM). Nevertheless, there is no consensus about the optimum energy desirable to disrupt the soil. We therefore aimed (i) to quantify the effect of varied ultrasonic energies on the recovery of each particle-size fraction and their C, N and δ13C distribution, and (ii) to determine an ideal energy to fractionate SOM of a specific soil. Our results show that the 2000–100 μm particle-size fraction was composed mainly of unstable aggregates and the 100–2 μm fraction of stable aggregates. Energies of 260–275 J ml−1 were sufficient to disrupt most of the unstable aggregates and leave stable aggregates. The use of this threshold energy combined with particle-size fractionation was not satisfactory for all purposes, since litter-like material and relatively recalcitrant organic carbon present in stable aggregates > 100 μm were recovered in the same pool. An ultrasonic energy of 825 J ml−1 was not sufficient to stabilize the redistribution of soil mass and organic matter among particle-size fractions, but at energies exceeding 260–275 J ml−1 relatively stable aggregates would fall apart and cause a mixture of carbon with varied nature in the clay fraction.

Summary To elucidate the mechanism of podzolization in its first stages we studied the fate of the water-soluble organic matter (WSOM) in incipient podzols in sandy soils by comparing the composition of the WSOM from L, F and H horizons with that in the bulk of the Bh horizons and fibres of three profiles. The WSOM appeared to consist significantly of ligno-cellulose and proteins, but these biopolymers were hardly present in the Bh horizons. The material of the fibres, however, greatly resembled the WSOM composition, thereby suggesting that in these soils most of the WSOM is transported through the B horizon and accumulates hardly changed in thin bands where the water stops moving. This implies that in the early steps of podzolization, accumulation of organic matter in the B horizon is not likely to be caused by water-soluble material.

The characteristic strong aggregation observed in Oxisols is usually attributed to the presence of free aluminium or iron compounds. Previous investigation of Oxisols from Minas Gerais, Brazil, suggested that iron oxide minerals do not necessarily play a role in aggregation. Oxisol profiles developed on different parent materials (rock-saprolites and sediments), and with different degrees of polygenesis, were investigated to assess whether the physical makeup, rather than the iron content, determines aggregation. Oxisols were investigated by means of micromorphology and laser diffraction grain-sizing. Grain-size distribution curves were determined after three pre-treatments: shaking with water; removal of organic matter; and removal of organic matter followed by deferration. Micromorphology indicated that soils developed on rock-saprolites have hematite droplets (discrete, red colored, equidimensional concentrations) in the saprolite, whereas droplets are not found in soils on Tertiary sediments. However, secondary iron accumulations related to periodic water saturation are encountered in the soils on sediments and not in the soils on rock-saprolites. Grain-size distribution curves showed that the Oxisols on rock-saprolites do not have strong aggregation because of iron oxides alone. Conversely, aggregation by iron oxides is evident in the Oxisols on sediments. This indicates that remobilization of iron during soil formation is essential for iron forms to play a role in aggregation. These findings suggest that the mode of formation and iron mineralogy affect aggregation.

Summary Podzols tend to form on drift sands in The Netherlands given sufficient time. Differences in organic matter (OM) composition relate to vegetation succession on drift sand that evolves eventually into a micropodzol. We examined the relation between the water-soluble organic matter (WSOM) and the total OM composition in the Ah horizons of the first vegetation stages, under grass (Corynephorus canescens), moss (Polytrichum piliferum), heather (Calluna vulgaris) and pine (Pinus sylvestris), as determined by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and analysis of polysaccharides after acid hydrolysis. Polysacharides dominate the OM in the Ah horizons under grass and moss. Lignin and aliphatic compounds are minor compounds in these profiles, but are more important under heather and pine. The Py-GC traces of the WSOM under grass and moss contain abundant products derived from polysaccharides. The water-soluble fraction is enriched in phenolic and aliphatic compounds in comparison with their contents in pyrolysates of the total OM. In the WSOM fractions under heather and pine, phenols dominate the pyrolysates, whereas lignin-derived methoxyphenols are rare. Remarkably large amounts of alkenes and alkanes are present in the pyrolysates of these water-soluble fractions, most probably derived from aliphatic biopolymers. Their presence in water might be explained through the formation of colloids, which are stabilized by micelle-like arrangements.

Grain sizes of eight profiles from a soil catena (640–3160 m) on andesitic ash in perhumid atlantic Costa Rica were investigated by laser diffraction grain-sizing. The samples were (1) shaken with water, (2) treated with peroxide, and (3) treated with peroxide–oxalate. Allophane is absent above 2000 m; it appears around 2000 m and increases downwards. Peroxide treatment and oxalate extraction indicate that the allophane fraction occurs in aggregates of well-defined sizes. The size of the allophane aggregates is between 2 and 20 μm, and it increases with increasing allophane content. Considerable crystalline clay fraction is only obtained upon oxalate extraction. Repeated oxalate extraction does not remove all allophane in high-allophane profiles. The method further allows the recognition of a large number of ash deposits and of recent ash additions, thus facilitating the recognition of stratified profiles.

Copyright (c) 1997 Elsevier Science B.V. All rights reserved. Cross-Polarisation Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance spectroscopy (CPMAS 13 C-NMR) represents one of the most powerful tools to investigate soil organic matter (SOM) mainly because of its inherent capacity to provide a semi-quantitative evaluation of carbon distribution. A critical parameter during acquisition of CPMAS 13 C-NMR spectra is the contact time required to obtain the cross-polarisation between proton and carbon nuclei. The procedure to evaluate the best contact time for the acquisition of a quantitative CPMAS 13 C-NMR spectrum is to perform Variable Contact Time (VCT) experiments. In this work the structural features of a number of purified humic substances from Italian and Costarican volcanic soils were investigated by CPMAS 13 C-NMR spectroscopy after having performed preliminary VCT experiments. The VCT experiments showed that the average contact times vary according to the origin and chemical structure of the humic material. The optimal contact times (OCT) for nine humic samples were between 250 and 800 μs. These values were different from the time of 1000 μs that is commonly applied as the best average contact time for humic materials. Moreover, by comparing the NMR data to those obtained by elemental analysis (C/H ratio), it appeared that the efficiency of the cross-polarisation between protons and carbons, and hence the contact time, is affected not only by the number of protons, but also by their distribution over the molecules. The evaluation of errors in quantitative estimation of the different carbons revealed that the use of OCT generally reduced by half the loss of signals occurring when the average contact time of 1000 μs is used in CPMAS 13 C-NMR spectra of humic substances.

A selection of plant species that may have been relevant for the Neolithic in the SW Mediterranean have been characterised with pyrolysis gas chromatography mass spectrometry (pyrolysis–GC/MS) in search for molecular vegetation markers. Roots and aerial parts were analysed separately for the following species: Anthyllis cytisoides, Asphodelus cerasiferus, Brachypodium retusum, Cistus albidus, Cistus clusii, Dorycnium pentaphyllum, Ephedra fragilis, Juniperus oxycedrus, Juniperus phoenicea, Olea europaea, Phillyrea angustifolia, Pinus halepensis, Pistacia lentiscus, Quercus coccifera, Rhamnus lycioides, Rosmarinus officinalis, Smilax aspera and Stipa tenacissima; furthermore domesticated plants were analysed, including wheat (Triticum aestivum, Triticum dicoccum, Triticum monococcum, Triticum timopheevi and Triticum turgidum), barley (Hordeum vulgare and H. vulgare Hulled) and legumes (Lathyrus cicera, Lathyrus sativus, Lens culinaris, Pisum sativa, Vicia ervilia, Vicia faba and Vicia sativa). This resulted in 290 potential markers. In addition, the organic matter of surface soils under different vegetation cover has been analysed to test the presence of the potential markers in the soil. Forty-six of the potential markers were detected in the soil organic matter, of which part have not been reported before. The results may be useful for interpretation of the organic matter composition of soils and plant remains, which can be valuable in archaeology.

A continuous section of hydromorphic to well-drained podzols in a Late Pleistocene marine terrace of southeastern Brazil offers a unique opportunity for a detailed interpretation of podzol morphology. The soils show very deep and homogeneously colored B horizons in the most hydromorphic members, where the predominant water movement in the B horizon appears to be lateral. Upon improving drainage, the effect of roots becomes evident by the increase in root-related E-horizon tongues, while the B horizon becomes shallower and shows a more pronounced accumulation of organic matter at its top. Only where the groundwater does not periodically reach into the B horizon, a homogeneous distribution of Fe is found in the Bs horizon. The sequence shows clear effects of decomposition of the B horizon through growth of the E horizon, sometimes leading to isolated remnants of the B horizon, on the fringes of which organic matter may accumulate. Especially the hydromorphic profiles show large mottles with roughly concentric structures in the B horizon where organic matter has been depleted. In the poorly drained members of the sequence, the effect of improved drainage by erosion of the cliff is visible in black instead of brown colors of the upper B horizon. In all profiles, the conversion of the former B horizon into an E horizon is accompanied by strong biological activity in the form of burrows.

The chemical composition of soil organic matter (SOM) following secondary succession in Imperata grassland was investigated by Pyrolysis-Gas Chromatography/Mass Spectrometry (GC/MS). We studied 46 samples from different stages of succession using plots that last burned 3 and 9 years previously, secondary forest (≥ 15 years), primary forest and Acacia mangium plantation (9 years). During regeneration of Imperata grasslands the chemical composition of SOM changes considerably. Differences between litters and SOM were larger than within SOM, which is mainly due to a rapid degradation of lignin in the soil. Both litter and SOM under Imperata contain larger amounts of carbohydrates and fewer lignin moieties, aliphatics and N-compounds than those under secondary and primary forest. Nevertheless, SOM degradation under grassland is less efficient because of scarcity of N-compounds. SOM decomposition is most advanced under forest, as indicated by lower amounts of plant derived compounds and higher contribution of microbial matter. Decomposition efficiency appears to be related to SOM chemistry, but more to abundance of N-compounds than to that of potentially recalcitrant compounds. C stocks were linked to decomposition efficiency and litter production.

The most common soils that occurred in environments generically called restinga are podzols that are characterized by the presence of spodic horizon (Bh or Bhm). There are few scientific studies related to the genesis of these soils in tropical regions, and there are few detailed studies assessing the chemical characteristics and composition of organic matter (OM) present in these soils, as well their relations with time. The cities Cananéia and Bertioga were selected for this research due to the presence of different sedimentary units and remaining vegetation. The characterization of humic acids (HA) was realized using spectroscopic techniques like Fourier transform infrared spectroscopy (FTIR) and fluorescence. Samples were extracted from different podzol horizons in order to achieve more details about the OM present in these soils and relate the results to the stability of carbon and the mean residence time (MRT) of OM. The main hypothesis tested was that the profiles where the OM has less MRT would have the highest contents of more recalcitrant compounds. In this context, the main results related to the objectives were as follows: The older profiles were those with the highest concentrations of more recalcitrant compounds, especially in the subsurface horizons (Bh and Bhm). This inference may indicate that with transcurrent time, OM tends to undergo changes in its composition and become recalcitrant.

Peat molecular chemistry reflects a combination of plant input and decomposition. Both vegetation community and the degree of decomposition of plant remains are highly dependent on depth and fluctuation of the water table and thus peat organic matter (OM) chemistry reflects past hydrological conditions. Changes in hydrology according to the OM composition (by pyrolysis-gas chromatography/mass spectrometry, pyrolysis-GC/MS) in a high-resolution sampled monolith of an 8000 years old peat deposit are presented. Analysis of 18 modern vegetation species resulted in molecular markers for Erica spp., Deschampsia flexuosa, Juncus bulbosus and Carex binervis, in addition to more general markers which enabled differentiation between woody, grass and moss vegetation. Factor analysis of 106 pyrolysis products quantified for all peat samples enabled identification of mineral (Factor 1) and hydrological (Factor 2) conditions of the bog. Depth profiles of vegetation markers showed good agreement with those of the scores of both factors and enabled the identification of 14 relatively wet periods, dating to 1430–1865 AD, 930–1045 AD, 640 AD, 270–385 AD, 190–215 AD, 135 AD, 45 BC–15 AD, 260–140 BC, 640–440 BC, 1055–960 BC, 1505–1260 BC, 2300 BC, 4190–2945 BC and 5700–5205 BC, which show excellent agreement with other palaeoclimatic studies in Europe. The results emphasize the importance of high-resolution sampling, in combination with the use of multiple vegetation markers and other peat OM characteristics for a proper interpretation of a peat record.