Search

Purpose: The objective of this study is to improve our understanding of soil organic matter (SOM) stability in Brazilian Cerrado, by interpreting soil properties at the ecosystem scale and elaborating on the interactions of biotic, climatic and edaphic controls. Methods: Three 2 m soil profiles with significantly different total organic carbon TOC content but located on the same geomorphological unit were studied for δ13C isotopic composition to connect tree-grass patterns to TOC content. To gain insight into soil carbon stability, C/N, δ13C and δ15N were analysed for functional organic matter (OM) pools: free particulate OM (POM), occluded POM, base-extractable OM, and mineral-associated OM. Results: Small but abrupt shifts of δ13C with depth reflected simultaneous changes in tree-grass vegetation patterns over the past 10,000 years in all three profiles. These temporal changes were superimposed on spatial differences as indicated by consistent differences in δ13C values between the profiles, reflecting that site-specific differences in tree-grass patterns persisted over the past 10,000 years. Profiles with a historically larger contribution from trees (as evidenced by lower δ13C) had increased charcoal contents. Downward movement of charcoal by intense bioturbation occurred faster in the OM-rich soils as suggested by 14C dating. Conclusion: We found that long-term carbon storage in Brazilian Cerrado soils was a conjunction of wildfires, bioturbation, and local edaphic controls on tree-grass composition. Soils with an OM-rich thick A-horizon had more trees, more charcoal, and a higher activity of soil macrofauna, which was related to local differences in soil water availability.

Aims: We investigated morphological variations in podzols caused by changes in soil porosity and permeability upon the growth of large tree-roots in a tropical barrier island (Ilha Comprida, Brazil). Methods: Soil morphology was described in a continuous lateral sequence of podzols on a 35 m-long cliff. A soil thin section was used to characterize organic matter (OM) accumulation and to estimate soil porosity, permeability, and saturated hydraulic conductivity (Ksat). Soil texture and the contents of organic carbon, Al, and Fe were determined for each pedogenic horizon containing large tree-roots. The evolution of podzol morphology was interpreted in the context of age determinations by optically stimulated luminescence and 14C. Results: Taproots of cashew trees (Anacardium occidentale) penetrated the cemented Bhm horizon and the massive-clayey 2Cgj horizon. Aligned with the taproot, we found a vertical OM-band with lower porosity, permeability, and Ksat than the adjacent Bh and E horizons. Irregular or broken boundaries between the E and Bh horizons were caused by large tree-roots. While the maximum age of these podzols is 3390 ± 530 years, significant and rapid changes in the Bh-horizon morphology occurred within the lifetime of the cashew trees (~ 50 years). Conclusions: The interplay between reduction in flow adjacent to large taproots and the enhanced vertical infiltration at depth has resulted into the development of irregular and broken boundaries between the E and Bh horizons. Because tree-roots alter both local soil porosity and water flow paths, they simultaneously cause the formation and degradation of podzol Bh-horizon.

The sorption of dissolved organic matter (DOM) depends on its interaction with the soil matrix. In hydromorphic podzols, DOM reacts mainly with aluminium (Al), which is responsible for the formation of the Bh-horizon in the subsoil. In this work, we investigated whether the retention of DOM in the soil during the podzolization process is selective in relation to the molecular composition of DOM. A column experiment was conducted to study the selective retention of sorption and desorption processes under controlled conditions. Materials used in the column experiment were representative for Brazilian coastal podzols under tropical rainforest. Materials were collected from this tropical coastal podzol ecosystem, and included soil from E- and Bh-horizons, and DOM from a stream (Stream), peat water (Peat), litter (Litter) and charred litter (Char). To evaluate selective retention of DOM, both the initial DOM and its leachates were analyzed by Fourier transform infrared spectra absorption (FTIR) and pyrolysis gas-chromatography/mass spectrometry (Py-GC/MS). The results showed preferential retention of DOM associated with biopolymers for soil columns with E-horizon material (E), E with Al nitrate (E-n), E with kaolinite (E-k) and E with gibbsite (E-h), except for Char. The composition of leachates after percolation through B horizon columns was mainly determined by desorption, and had a relatively large contribution from phenolic and carboxylic groups associated with Al and low molecular weight aromatic and N-containing pyrolysis products, while products from macromolecular materials such as cellulose were selectively retained in the columns for all DOM types. DOM from the Stream (taken during the rainy season) resembled that of desorbed OM from the B columns, reinforcing substantial desorption in the field as well. Our results suggest that sorption and desorption of OM in the hydromorphic Bh-horizon is continuous and that the selectivity of sorption is dependent on DOM source.

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.

Peatlands are archives of environmental change that can be driven by climate and human activity. Proxies for peatland vegetation composition provide records of (local) environmental conditions that can be linked to both autogenic and allogenic factors. Analytical pyrolysis offers a molecular fingerprint of peat, and thereby a suite of environmental proxies. Here we investigate analytical pyrolysis as a method for biomarker analysis. Pyrolysates of 48 peatland plant species were compared, comprising seventeen lichens, three Sphagnum species, four non-Sphagnum mosses, eleven graminoids (Cyperaceae, Juncaceae, Poaceae), five Ericaceae and six species from other families. This resulted in twenty-one potential biomarkers, including new markers for lichens (3-methoxy-5-methylphenol) and graminoids (ferulic acid methyl ester). The potential of the identified biomarkers to reconstruct vegetation composition is discussed according to their depth records in cores from six peatlands from boreal, temperate and tropical biomes. The occurrence of markers for Sphagnum, graminoids and lichens in all six studied peat deposits indicates that they persist in peat of thousands of years old, in different vegetation types and under different conditions. In order to facilitate the quantification of biomarkers from pyrolysates, typically expressed as proportion (%) of the total quantified pyrolysis products, an internal standard (5-a-androstane) was introduced. Depth records of the Sphagnum marker 4-isopropenylphenol from the upper 3 m of a Sphagnum-dominated peat, from samples analysed with and without internal standard showed a strong positive correlation (r2 = 0.72, P

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.

The formation of sombric horizons (dark horizons in the subsoil) is still not understood. In order to improve our understanding of the formation of sombric horizons we studied these soils in southern Brazil from various perspectives. The lateral configuration and grain size distribution excluded the possibility that the sombric horizon is a paleosol covered by an eolian deposit or colluvium. Micromorphology showed intense biological activity, indicating strong bioturbation. The absence of clay and OM coatings indicates that the sombric horizon in the study area was not formed by illuviation. Considering changes with depth, phytoliths and δ13C isotopes clearly showed that the OM from the sombric horizon had a larger contribution from grasses, while a larger contribution from black carbon (BC) was evidenced by the molecular composition. A larger contribution from grasses and BC both correspond to drier climatic conditions. However, similar depth trends for δ13C and PAHs were found in the reference profile (without sombric horizon), in agreement with climatic change but not explaining the different morphology. The molecular composition and C/N ratio showed that the profiles differed in degree of decomposition, with the OM in the soils that contained a sombric horizon being more decomposed than that in the reference profile. The sombric horizon is thus a remnant of an earlier phase of soil formation under a drier climate, which is made visible by differences in decomposition of OM related to subsequent more humid conditions. Stronger decomposition in the profiles with a sombric horizon may be related to better drainage, explaining their occurrence in the highest positions within the landscape and suggesting a topographic control.

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.

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.

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.

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.

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) dynamics upon secondary succession in Imperata grassland was studied by stable carbon isotope analysis. The data of litter and soil samples of twenty plots in four different stages of succession were compared. These different stages were represented by plots that were; (1) last burned 3 years before sampling (Imperata grassland), (2) last burned 9 years before, (3) a secondary forest (≥15 years) and (4) a primary forest. Result showed that isotopic signatures of all soil horizons of the regeneration stages were statistically different from those of the primary forest. The A-horizon under the 3-years Imperata plot still contained 23% forest (C3) carbon, and this fraction increased to 51% in the-B-horizon. In the 9-years plot and in the secondary forest, the C3 carbon on the A-horizon increased to 51% and 96%, respectively. In the topsoil, the loss of C4-C between the 3-years and the 9-years plot was significant, while it appeared negligible in the AB-horizon. The strong decay in the topsoil under Imperata grassland may be due to the rather high carbohydrate content of the SOM, which is considered easily decomposable. Further research is needed especially to explore the relation between carbon stocks and chemical of SOM composition. Such insight may help to better understand and predict soil carbon changes in relation to climate and vegetation change.

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.

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.

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.

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.

To evaluate correlations between silt and clay fractions determined by pipette method and laser diffraction, samples from Dutch fine marine, fluvial, and loess deposits were analysed by both methods. For fluvial deposits, correlations for fractions 50 μm were excellent (R2 > 0.95), those for 2–4, 4–8, 16–32 and 32–50 μm were satisfactory (R2 = 0.80 – 0.95), while that for the fraction 8–16 μm had an R2 of only 0.68. For marine deposits, correlations for 50 μm were in the same range, but those of all other fractions except 8–16 μm were lower. In the loess samples, correlations for all but the 8–16 μm fraction were unsatisfactory. Laser diffraction gave 42% of pipette clay in marine samples, and 62% in fluvial and loess samples if regressions are forced through 0. Sand fractions detected by laser diffraction were 107% of the sieve fraction in marine samples, and 99% in the fluvial samples. Correlations for fractions smaller than reference size are generally better than those for individual size fractions. Both the 2 μm and the 50 μm boundary cause problems in the comparison. The first because of platy shape of clay minerals, and the second due to both a change in method in the pipette/sieving procedure, and to non-sphericity of particles. Apparently, correlations for clay- and silt-size fractions obtained by pipette method and laser diffraction will be different for each type of sediment.

The geomorphic evolution of the south-eastern Brazilian landscape is attributed to climatic changes coupled with tectonic activity. Soils developed on the resulting surfaces are mainly deep polygenetic Oxisols. The combination of stable landscapes (with continuously exposed soils) and neo-Cenozoic graben zones (episodically filled with sediments that may have undergone soil formation) offers the possibility to unravel the history of the soils that are found at the present day surface. Soil-sediment sequences in the southern part of the state of Minas Gerais, Brazil were investigated by micromorphology and mineralogy in order to understand the genesis of the soils. Erosion (profile thinning), weathering, biological activity, clay accumulation and iron translocation are the main soil forming processes imprinted in the various pedosedimentary layers. Strong weathering is shown by dissolution of quartz and weathering of ilmenite. Bioturbation is ubiquitous even in older and deeper buried layers. Clay accumulation is observed as illuviation and precipitation features which were micromorphologically differentiated. Accumulation and movement of iron are represented by gley and pseudogley features, related to groundwater and surface-water saturation processes. These features and the layering of sediments and soils play key roles in understanding the evolutionary phases undergone by the soils and sediments. As main soil formation episodes, the graben fillings show two phases of clay formation and illuviation, separated by a phase of ferralitization, interrupted by various episodes of erosion. The whole material was eventually overprinted by a phase of ferralitization and plinthite formation. Apart from water saturation, these processes also appear to have acted on the soils of the stable areas (not affected by tectonic activity), but overprinting and erosion prevents recognition of the separate evolutionary phases.

Reactie op het artikel van ED van Riessen en N. Vandenberghe in Geologie en mijnbouw (1996), p 301 ev.

Analytical pyrolysis-GC/MS and solid-state 13C NMR (nuclear magnetic resonance) were applied to the NaOH-extractable organic matter fraction of a colluvial soil from Galicia (NW Spain) that represents more than 8500 yr of accumulation. While molecular indicators of vegetation change were looked for, it seemed likely that any such signal was disturbed by the intense fire regime of the area. This conclusion was drawn from (1) the presence of three charcoal layers, (2) the high proportion of aryl C in NMR spectra (non-quantitative) and (3) the prevalence of benzenes and polycyclic aromatic hydrocarbons (PAHs) in the chromatograms (38 ± 6% of total identified peak area), also in charcoal-poor samples. If this conclusion is accurate, the area has been subjected to burning episodes for at least 8000 yr. Additionally, the results indicate that biomass burning residues (black carbon; BC) may become NaOH extractable after long periods of degradation in mineral soil. These results add to our knowledge of the long-term fate of BC in soil, which is a potential agent in the global C cycle., Project supported by the "Plan Nacional: Paleopaisaje y prehistoria del Futuro Parque de Arte Rupestre de Campo Lameiro, Pontevedra" (PGIDT02CCP60601).

In geologically stable areas in the tropics, climatic changes and geomorphic cycles give origin to polygenetic soils. Polygenesis involves new soil formation phases taking place on preweathered materials from previous phases, resulting in soils with rather similar chemical and mineralogical properties. Polygenetic soils from Minas Gerais, Brazil, were investigated with the purpose of distinguishing mineralogical aspects in relation to polygenesis. The soil materials were studied by micromorphology and electron microscope and analyzed by XRD. All soils are strongly weathered and even show weathered grains of ilmenite and quartz. The soils show two phases of kaolinite formation (pseudomorphs after mica and precipitation from solution) and of accumulation of iron compounds. Desilication causes gibbsite formation from kaolinite, occasionally even in the deep saprolite. Superposed processes can be due to progressively deeper weathering or to changes of the external environment.

The most frequent soils in the São Paulo State Coastal Plain are Podzols, characterized by strong to moderate hydromorphic to well-drained podzolization with very well developed podzol-B horizons (Bh or Bhm). Podzolization processes include the effects of hydrology and rooting on profile morphology and the subsequent effects of improved drainage. A Podzol chrono-hydrosequence was described in detail on a cliff at the south coast of Ilha Comprida, a Holocene barrier island, and allowed a subdivision into four distinct groups: poorly-drained profiles, profiles with well-drained B horizons, strongly rooted profiles and superposed profiles. The morphological description and some observations about the exposure cliff were essential for grouping and differentiating the podzol profiles. Some well-drained podzols have OM-depleted mottles that are related to selective decomposition of organic matter (OM) by microorganisms. Such mottles are frequently associated to root channels. Seventeen profiles were studied, thirteen had depletion mottles scattered along the profile. Most of these mottles are whitish and are located preferentially in the horizons of transition between the E and B horizons, particularly in conditions of good drainage. Such mottles have certain morphological differences and may be grouped according to similarities in their morphology and their position in the profile. Distinct groups are: (a) concentric OM-depleted mottles; (b) circular/tubular OM-depleted mottles (burrows); (c) dotted OM-depleted mottles; (d) ghost OM-depleted mottles; (e) irregular OM-depleted mottles and (f) Fe-depleted mottles. The chemical composition of soil organic matter was studied in detail using pyrolysis in combination with gas chromatography/mass spectrometry (Py-GC/MS). Samples of all horizons of the distinct profiles studied were taken, as well as from the center of the mottle (M) and from the direct surroundings (S). The processes involved in the genesis of Podzols in the sandy coastal plain are directly related to drainage, the contribution of dissolved organic matter (DOM), the contribution of organic matter derived from roots, the chemical composition of organic matter and its decomposition by microorganisms, causing a large variation in adjacent Podzols. The well-drained Podzols differ in characteristics from the poorly drained ones in composition and deposition of OM, as well as its decomposition, which is directly related to the activity of groups of microorganisms. They also differ in the relative contribution of OM-derived from roots and DOM. There is a wide variation in the characteristics of decomposition by microorganisms between the profiles of Podzols permanently exposed to air and marine spray (the cliffs) on Ilha Comprida and those inland (pits). There are therefore two main processes that change the morphology of Podzols (OM and composition): (a) change in drainage and rooting, and (b) exposure to air. Os solos mais frequentes na Planície Costeira do Estado de São Paulo são os podzóis, caracterizados por podzolização com hidromorfismo forte a moderado a bem drenado com horizontes B-podzol muito bem desenvolvidos (Bh ou Bhm). O processo de podzolização inclui os efeitos da hidrologia e do enraizamento no perfil e os efeitos subsequentes da drenagem melhorada. Uma crono-hidrosequencia de podzóis foi descrita em detalhes em um barranco na costa sul da Ilha Comprida, uma ilha barreira do Holoceno, e permitiu uma subdivisão em quatro grupos distintos: perfis mal drenados, perfis com horizonte B bem drenados, perfis fortemente enraizados e perfis superpostos. A descrição morfológica e algumas observações sobre o barranco exposto foram essenciais para o agrupamento e diferenciar os perfis de podzóis. Alguns desses podzóis bem drenados possuem manchas esbranquiçadas que estão relacionadas com a seletiva decomposição da matéria orgânica (MO) por microorganismos. Tais manchas são freqüentemente associadas aos canais radiculares. Foram estudados dezessete perfis, dos quais treze apresentaram manchas de esgotamento espalhadas ao longo do perfil. A maioria destas manchas são esbranquiçadas e estão localizadas preferencialmente nos horizontes de transição entre os horizontes E e B, particularmente em condições de boa drenagem. Tais manchas possuem algumas diferenças morfológicas e puderam ser agrupadas de acordo com semelhanças na sua morfologia e da sua posição no perfil. Os grupos são: (a) manchas concêntricas de depleção da MO; (b) manchas circulares/tubularess de depleção da MO (tocas); (c) manchas pontilhadas de depleção da MO; (d) manchas fantasmas de depleção da MO; (e) manchas irregulares de depleção da MO; e (f) manchas de depleção de Fe. A composição química da matéria orgânica do solo foi estudada em detalhe por pirólise em combinação com cromatografia em fase gasosa/espectrometria de massa (Py-CG/EM). Amostras de todos os horizontes dos perfis estudados foram coletadas, bem como amostras do centro das manchas (M) e do solo adjacente (S). Os processos envolvidos na gênese de podzóis da planície costeira arenosa estão diretamente relacionados com a drenagem, a contribuição de matéria orgânica dissolvida (MOD), a contribuição de matéria orgânica derivada de raízes, a composição química da matéria orgânica e sua decomposição por microorganismos, causando uma grande variação no podzóis. Os podzóis bem drenados diferem em características dos mal drenados em composição e deposição de MO, bem como a sua decomposição, que está directamente relacionada com a actividade dos grupos de microrganismos. Eles também diferem na contribuição relativa da MO derivada de raízes e MOD. Existe uma grande variação nas características da decomposição por microorganismos entre os perfis de podzóis permanentemente expostas ao ar e spray marinho (falésias) na Ilha Comprida e os do interior (trincheiras). Há, portanto, dois processos principais que alteram a morfologia de podzóis (composição da MO): (a) mudança na drenagem e enraizamento, e (b) a exposição ao ar.

Solos com horizonte A escurecido, com presença de artefatos humanos como cerâmicas, ossos e/ou conchas, alta saturação por bases, carbono orgânico e carvões são denominados comumente de Terras Pretas de Índio (TPI), de ampla ocorrência na região Amazônica. Tais características tornam estes solos muito favoráveis para o cultivo agrícola, sobretudo pelo elevado conteúdo de matéria orgânica do solo (MOS). No entanto, dentre as questões ainda não desvendadas quanto à gênese destes solos, está a natureza e mecanismos de retenção desta matéria orgânica nas TPI. Nesse sentido, o objetivo deste trabalho foi elucidar a natureza química da MOS em solos com horizonte A antrópico e em solos de referência (sem horizonte A antrópico). Para isso, dois perfis de TPI e um perfil de referência foram selecionados na área do Campo Experimental do Caldeirão no município de Iranduba - AM. Amostras de todos os horizontes foram coletadas e submetidas ao fracionamento físico e químico da matéria orgânica, gerando as frações: i) (FLL); ii) Leve oclusa (FLO); iii) extraível com NaOH (EX) iv) Resíduo (RES). Todas elas foram caracterizadas por meio da pirólise CG/EM. A FLL e EX estão presentes em quantidades maiores nas TPI, devido, respectivamente, ao maior imput de mateiral fresco promovido intencionalmente pelo homem nestas áreas e à maior humificação deste material. Por outro lado a FLO foi maior no perfil de referência. A FLL possui alta expressão da liteira, sendo constituída, sobretudo por materiais vegetais e carvões. A FLO teve alta variabilidade composicional, no entanto de modo geral possui semelhança com a FLL, mas é menos enriquecida em derviados do BC (compostos poliaromáticos) e maior quantidade de material vegetal fresco (ligninas). No entanto, esta fração contribui muito pouco para o carbono total do solo. Entre os diferentes perfis, a principal diferenciação ocorreu na FLL, que possuiu menos levoglucosan e mais poliaromáticos nos perfis antrópicos, o que mostra, portanto, condições mais avançadas de mineralização e enriquecimento relativo em BC. No entanto, no geral há maior abundância de compostos aromáticos nos perfis de TPI, demonstrando maior contribuição de BC. A fração do resíduo mostrou, grande contribuição de compostos alifáticos. No entanto quando compara-se os diferentes perfis, as TPI são enriquecidas com compostos poliaromáticos, reforçando novamente a contribuição do BC. Não foi possível, com os métodos de extração e fracionamento utilizados, afirmar se os produtos derivados do BC nesta fração estão realmente ligados a fração mineral ou estão presentes no RES por serem insolúveis em alcalino. Nesse sentido, conclui-se que há uma grande contribuição do BC para a estabilização (pelo mecanismo da recalcitrância química) da MO nos perfis de TPI nas diferentes frações e, além disso, verificou-se também nestes perfis estágios mais avançados de decomposição, concordando com o fato de que nas TPI há um maior grau de humificação da MO. The Anthrosols known as Amazon Dark Earths (ADE) are peculiar soils found in Amazonian Forest, presenting dark coloured A horizons that combine the following features: presence of human artefacts, bones and shells; high levels of organic carbon and coal; and a high base saturation index. Such characteristics are an advantage for agriculture practices, even in the current days. However, their genesis mechanisms are still poorly understood, especially the processes related to organic matter fixation. This contribution aims to elucidate the chemical nature of soil organic matter (SOM) in some Anthrosols and reference soils (without Anthropic A horizons), comparing two pedons with the referred characteristics in the county of Iranduba (Amazon State, Brazil). Soil samples were physically and chemically fractioned, into the following groups: i) FLL, ii) light occluded (FLO), iii) NaOH extractable (EX); iv) residual (RES). SOM samples were chemically characterized using the CG/EM pyrolysis technique. The FLL and EX fractions are more common in IDA soil samples due to the high inputs of fresh plant materials intentionally introduced by human groups in the past, and to the high degree of humification. The FLO fraction was higher in the reference soil samples (without Anthropic A horizons). The FLL fraction was more expressive in the litter samples, consisting of plant materials and coal. The FLO fraction presented a high compositional variability but similar to FLL fraction, less enriched in polyaromatic compounds (BC) and fresh plant materials (lignin). Nevertheless, this fraction represents a minor contribution to total organic carbon of soils. Within the different pedons, the main difference was observed in the FLL fraction, less enriched in levoglucosan and polyaromatic compounds in the Anthrosols. It suggests a rapid mineralization of organic matter and high contribution of BC compounds in these soils. In general, the BC compounds are a major control in Anthrosols. The residual fraction shows high levels of aliphatic compounds. However, in the Anthrosols the BC compounds maintain a high level. It was not possible to determine whether the BC bearing compounds are bound to the mineral fraction or belong to RES fraction (low solubility in high pH values). The BC compounds must contribute significantly to SOM stabilization in the different fractions of Anthrosols pedons (chemical recalcitrance mechanism). Moreover, decomposition degree of SOM is higher in the Anthrosols, in agreement to the high degree of humification.

A vegetação de restinga é uma formação típica que ocorre na costa brasileira em materiais de origem quartzosos e pobres em nutrientes. O principal processo pedogenético que ocorre nos solos sob essa vegetação é a podzolização, sendo os Espodossolos e os Neossolos com podzolização incipiente os solos mais comumente encontrados. A podzolização é freqüentemente estudada em regiões de clima frio, sendo escassos os estudos dos mesmos em clima tropical e desenvolvidos sobre sedimentos marinhos quartzosos. Foram coletados e descritos morfologicamente nove perfis de solos sob vegetação de restinga na Ilha do Cardoso-SP com o objetivo de caracterizá-los em sua química, física, morfologia, mineralogia e estudar a dinâmica do Fe e do Al nestes solos com o intuito não só de se compreender melhor a gênese dos mesmos como para contribuir com o aprimoramento do Sistema Brasileiro de Classificação de Solos (SiBCS). Os resultados mostraram solos hidromórficos, arenosos, muito ácidos, com teores variáveis de matéria orgânica e fases não cristalinas Al e Fe, sendo que o Al é o metal que participa mais efetivamente do processo de podzolização, o qual é altamente dependente da hidromorfia. Este fato é evidenciado pela microtopografia, que exerce papel importante na distribuição dos solos. Foi identificada pirita em alguns horizontes (2Cgj), os quais apresentam características distintas em relação aos demais, tais como textura mais fina e presença de esmectita. Este material de origem influencia até os horizontes espódicos, reduzindo o pH bruscamente na determinação da TFSA (terra fina seca ao ar), devido à influência indireta promovida pelo lençol freático. Nos horizontes espódicos, os principais minerais encontrados foram o feldspato e o quartzo na fração silte e a caulinita e o quartzo na fração argila, evidenciando uma assembléia mineralógica mais pobre em relação a outros Espodossolos de clima frio e até mesmo em relação a outros da costa brasileira. Isso ocorre devido principalmente ao próprio material de origem ser muito pobre em minerais primários intemperizáveis. O SiBCS mostrou falhas na classificação da ordem Espodossolos a partir do 2º nível categórico (subordem), principalmente no que diz respeito ao acúmulo de Fe no horizonte espódico. Sugerese a inserção da denominação "tiônico" no quarto nível categórico, devido à possibilidade da ocorrência de solos tiomórficos, se forem drenados, bem como a adoção de um critério químico na distinção das subordens dos Espodossolos. As relações Carbono/Metal evidenciaram a baixa participação do Fe, sendo o Al o responsável pela precipitação química do complexo organometálico. Os Espodossolos estudados são holocênicos e a podzolização é dependente da hidromorfia. A presença de sulfetos de ferro afeta parte dos solos estudados e pode coincidir com horizontes espódicos. Restinga vegetation is a typical formation that occurs in brazilizan coast, on quartzitic, sandy poor parent material. The main pedogenic process that occurs in soils under this vegetation is the podzolization, being the Spodosols and Quartzipsamments, with incipient podzolization, the most common soils. Podzolization is frequently studied in regions of cold climate, with a lack of studies in tropical climate and quartzitic material. Nine soil profiles under restinga vegetation at Ilha do Cardoso, São Paulo State, had been sampled and morphologically described with the objective to proceed chemical, physical, morphological and mineralogical characterization and study Fe and Al dynamics in these soil with the aim of better comprehend its genesis, as well as contribute to an improvement of the Brazilian System of Soil Classification (SiBCS). The results had shown aquic, sandy, very acid soils with variable contents of organic matter and Al and Fe non crystalline phases. Al appears to be the metal that participate more effectively on podzolization process, which is highly dependent on aquic conditions. Being so, microtopography plays an important role in soil distribution. Pyrite and smectite was also identified in clay horizons (2Cgj) related to a distinct parent material. This material also influences spodic horizon chemistry generating low pH values in dried samples due to water table effects. Spodic horizons are mainly constitute by feldspar and quartz, in the silt fraction, and kaolinite and quartz, in the clay fraction, evidencing a poor mineralogical assembly in relation to other Spodosols of cold climate and even to those of Brazilian coast. This mainly occurs due to parent material which presents few weatherable primary minerals. SiBCS showed imperfections in the classification of Spodosols from 2nd categorical level (suborder), mainly because the absence of a chemical criteria for Fe accumulation in spodic horizon. We suggest the insertion of "thionic " denomination in the 4th categorical level because of the possible formation of acid sulphate soils in response to drainage, as well as the adoption of a chemical criteria in the distinction of subordens of Spodosols. Carbon/Metal ratios had evidenced low participation of Fe, being Al responsible for chemical precipitation of organo-metallic complex. Our Spodosols are holocenic and podzolization process depends on aquic conditions. Presence of iron sulfides affects some of the studied soils an also coincide with spodic horizons.

The peatlands are ecosystems extremely sensitive to changes in hydrology, and are considered as faithful \"natural archives of ecological memory\". In the Serra do Espinhaço Meridional, Minas Gerais State, Brazil, mountain peatlands has been studied by soil scientists, but until now multi-proxy studies are almost absent. The location of these peatlands is ideal because they are in an area influenced by the activity of the South America Monsoon Systems (SAMS), which controls the amount and distribution of annual rainfall. The aim of this work was to reconstruct the environmental changes occurred throughout the late Pleistocene and Holocene, both at the local and regional scale by using a multi-proxy approach (stratigraphy, physical properties, 14C and OSL datings, pollen and geochemistry). However, determining of the processes involved in the genesis and evolution of peatlands soils was also necessary step. The physico-chemical properties and elemental composition of five peat cores (PdF-I, PdF-II, SJC, PI and SV) from four selected mires (Pau de Fruta, São João da Chapada, Pinheiros and Sempre Viva) seem to have responded to four main processes: relative accumulation of organic and mineral matter, linked to the evolution of the catchment soils (local erosion); deposition of dust from distant/regional sources; preservation of plant remains; and long and short-term peat decomposition. The combination of proxies of PdF-I core defined six main phases of change during the Holocene: (I) 10-7.4 cal kyr BP, wet and cold climate and soil instability in the mire catchment; (II) 7.4-4.2 cal kyr BP, wet and warm with catchment soils stability and enhanced deposition of regional dusts; (III) 4.2-2.2 cal kyr BP, dry and warm and a reactivation of soil erosion in the catchment; (IV) 2.2-1.2 cal kyr BP, dry and punctuated cooling, with enhanced deposition of regional dusts; (V) 1.2 cal kyr-400 cal yr BP, sub-humid climatic and the lowest inputs of local and regional dust and the largest accumulation of peat in the mire; and (VI)

Uma evidência contundente da ocupação pré-histórica na Amazônia são os solos de cor escura com material arqueológico, conhecidos regionalmente como Terra Preta de Índio (TPI). Apesar de amplamente estudados, alguns de seus atributos permanecem ainda pouco conhecidos, especialmente os micromorfológicos, mineralógicos e geoquímicos. Esses estudos podem identificar os processos envolvidos na gênese e evolução desses solos, e quando empregados em conjunto com estudos fitolíticos, podem auxiliar na elucidação das suas formas de uso pretéritas. O objetivo desse estudo foi obter uma aproximação da hierarquia dos processos envolvidos na gênese desses solos e as suas prováveis formas de uso em tempos pré-colombianos. A pesquisa foi conduzida no Campo Experimental do Caldeirão, Iranduba - AM. Foram estudados dois perfis com TPI (P1 e P2) e um solo adjacente com horizonte A moderado (P3). Em cada horizonte foram coletadas amostras deformadas para análises físico-químicas, mineralógicas e geoquímicas e a cada 5 cm de profundidade para análise fitolítica e isotópica. Lâminas delgadas de amostras indeformadas de horizontes selecionados foram confeccionadas e descritas em sua micromorfologia, com posterior exame em microscópio eletrônico de varredura com microanálise química. A idade dos solos foi estabelecida com base em datações 14C de carvões. A microestrutura granular das TPI é de origem zoogenética e geoquímica. A gênese dos horizontes antrópicos envolveu: i) a ação do homem descartando e queimando resíduos (antropização); ii) espessamento do horizonte A e escurecimento dos horizontes subsuperficiais por bioturbação (cumulização e melanização); iii) dispersão e translocação de colóides (argiluviação); iv) condições pedoambientais diferentes das atuais (pedorrelíquia - nódulos ferruginosos). Revestimentos de argila com extinção forte, contínua e estriada nas cerâmicas indica que o processo de argiluviação é atual. O processo de elutriação predomina no solo não antrópico. A degradação dos nódulos de ferro na TPI favorece a xantização e atua como fonte de argila (pedoplasmação). Arecaceae e Cyperaceae são mais abundantes nos horizontes antrópicos, notadamente nos níveis com maior quantidade de cerâmica. A ausência de fitólitos de plantas domesticadas indica que a formação das TPI não está relacionada com práticas agrícolas. As evidências fitolíticas demonstram que as atividades antrópicas ocorreram de forma mais intensa no P1. A rápida ciclagem de silício, evidenciada pela presença de fitólitos com silicificação incompleta, favorece a estabilidade da mineralogia caulínitica. VHE, ilita e variscita-estrengita ocorrem somente nos perfis com TPI. P2O5-CaO-K2O-NaO-Cs-Co-Zn-Cu-Ba-Rb-Ni representa a assinatura geoquímica das TPI. A presença de variscita-estrengita, tridimita e maghemita nas TPI, notadamente nas cerâmicas, confirma a formação de minerais em decorrência das práticas antrópicas. As cerâmicas apresentam predominantemente cauixi (Tubella reticulata e Parnula betesil) e cariapé (Licania utilis). A presença comum de micas primárias nesses artefatos sugere material alóctone em seu fabrico. As TPI resultam da adição de artefatos arqueológicos e melanização de horizontes pedogenéticos não antropizados. Tais atividades enriqueceram em nutrientes e alteraram a assinatura geoquímica do solo, assim como promoveram a formação de minerais. Essa antropização acelerou os processos de argiluviação e de degradação de petroplintitas. No decorrer de sua evolução, foram utilizados e adicionados resíduos de plantas, destacadamente de palmeiras e Cyperaceae. A remarkable evidence of human occupation in Amazonian region is the existence of soils with dark colors and presence of ceramic materials, known as Indigenous Dark Earth (IDE). Despite of widely studied some of their features are still poorly understood, mainly that related to micromorphology, mineralogy and geochemical aspects. Such approach, in combination to phytolytic studies, is able to identify soil genesis processes and unravel the comprehension of occupation mechanisms of human. The aim of this study was to establish the hierarchy of these processes and their association with ancient activities of pre-Columbian populations. The research was carried out in the experimental site of Caldeirão, Iranduba city (Amazon state, Brazil). Two pedons containing surface anthropogenic horizons (P1 and P2) were directly compared to a non-anthropogenic soil (P3). In each soil horizon disturbed soil samples were sampled in order to perform physical, chemical, mineralogical and geochemical analyses. For phytolitic analyses samples were taken each 5 cm of depth. Micromorphological samples were studied in thin sections in the optical microscope and further analyzed in Scanning Electron Microscopy (SEM). The chronology was accomplished after 14C dating. The microaggregates in anthropogenic horizon are related to geochemical and biological processes. The genesis of IDE implicates in the following mechanisms: i) disposal and burning of residues by humans (anthropization); ii) deepening A horizons and darkening subsurface horizons by bioturbation (cumulization and melanization processes); iii) dispersion and migration of colloidal particles leading to argiluviation process; iv) different condictions of environment that not occur nowdays (pedorelict - ferruginous nodules). Clay coatings with extinction bands and continuous orientation in the ceramic artifacts suggest a current argiluviation process. The degradation of Fe nodules enhances the xantization process also providing clay (source of clay). The prevalent soil genesis in non-anthropic soil is the elutriation. The degradation of Fe nodules in the IDE enhances the xantization process also providing clay (pedoplasmation). The number of phytoliths of Arecaceae and Cyperaceae is higher in IDE than non-IDE, mainly in the horizons with more ceramics. The phytolitic evidence demonstrate that activities anthropic was more intense in the P1. The rapid Si cycling, highlighted by the presence of phytoliths without complete silicification, contribute to stability of kaolinitic mineralogy. HIV, illite and variscite-strengite are constrained to IDE pedons. P2O5-CaO-K2O-NaO-Cs-Co-Zn-Cu-Ba-Rb-Ni represents the geochemical signature of IDE. The presence of maghemite, variscite-strengite and tridimite strengthen a mineral forming process linked to human activity. In ceramic materials there is a prevalence of phytoliths from cauixi (Tubella reticulata and Parnula betesil) and cariapé (Licania utilis). The presence of mica suggests an alloctone material for their manufacturing. Hence the anthropic horizons result from the addition of archeological artifacts and melanization of non-anthropic horizons. These activities chemically enriched and modify the geochemical signature of soil, as soon as promoted formation of minerals. The anthropic activities conducted the argiluviation and degradation of Fe nodules. During their evolution there was a clear addition of plant residues, notably related to palm trees and Cyperaceae species.

The molecular composition of organic matter in peatlands reflects local conditions and stores information about botanical composition (plant source) as well as the degree of and conditions during decomposition. A reliable hydrological (and hence palaeoclimatological) interpretation of source and decomposition proxies in peatlands requires the understanding of the interactions between decomposition and botanical composition and the reaction of both to changes in the water table. Only few studies combined vegetation and decomposition characteristics to investigate peat OM dynamics and reconstruct environmental changes, and these included only a limited number of samples. In order to study the three-way relationship between botanical composition, decomposition and environmental conditions, pyrolysis-GC/MS of high-resolution sampled peat cores was used on two contrasting ombrotrophic peatlands. The two sites comprise a Sphagnum-dominated peatland in Tierra del Fuego (Argentina) and a graminoid-dominated peatland in Galicia (Spain). The purpose of this study was to examine the use of analytical pyrolysis in the environmental interpretation of peat profiles and to gain an improved understanding of peat OM dynamics and thereby develop parameters that reliably reflect past environmental conditions.The molecular composition of the Sphagnum-dominated Harberton peatland was first explored for a selection of samples. Several peat fractions have been analysed, including NaOH-extract, NaOH-insoluble residue and bulk sample. A large number of pyrolysis products was identified and quantified for all peat samples; additionally total C, N and ash content were measured. Molecular parameters were identified by a systematic methodological approach. Peatland plants have been analysed in search for specific markers. Factor analysis was used to reduce the number of pyrolysis products for quantification and to assess differences in peat chemistry and relate these to environmental factors. This resulted in a number of molecular parameters that reflect botanical changes, (an)aerobic decomposition and fire incidence.The results of the different peat fractions and plant analysis were applied to a large number of bulk samples (67), and used to reconstruct the 12,000 years of vegetation history of the Harberton core, which was then interpreted in terms of past hydrological conditions. The C:N ratio showed a perfect agreement with the botanical composition according to pyrolytic plant markers. It appeared that the n-alkane distribution showed remarkable changes with respect to shifts in the abundance of Sphagnum. Consequently, the detailed vegetation reconstruction was used to discuss the application of the n-alkane distribution in ombrotrophic peat. The simultaneous effects of botanical shifts (source material) and decomposition may cause conflicting hydrological interpretations for non-specific plant markers such as n-alkanes. The results indicated a considerable effect of aerobic decomposition on the distribution of n-alkanes. Although pyrolysis is not the regular method to establish the n-alkane distribution, comparison of n-alkanes in the NaOH-extract and residue peat samples supported the findings. The results emphasise the importance of combining vegetation and decomposition characteristics.For the graminoid-dominated Penido Vello peatland, all 101 bulk peat samples of the 3 m thick peat deposit have been analysed. In addition to the search for specific compounds of peatland plants, the same pyrolysis products were quantified for plant pyrolysates and peat. Depth records of plant markers agreed well with their preferential habitat, with the degree of decomposition and with the transition from minerotrophic to ombrotrophic peat. Factor analysis was used to reconstruct past hydrology. The results showed the importance of high-resolution sampling through the higher correlations between molecular parameters in the part sampled each 2 cm compared to 5 cm. Furthermore, good correlations of pyrolysis results were found with mineral content, solid-state 13C CPMAS NMR data and total N.The hydrological reconstruction based on depth records of plant markers and factor scores obtained by factor analysis of all quantified pyrolysis products, and the low contribution of Sphagnumto the graminoid-dominated Penido Vello peat allowed studying the effects of source and decay on the lignin composition. A large number of lignin pyrolysis products were quantified for peatland plants and for the three different peat fractions for a selection of 15 samples. Lignin composition of woody and graminoid plant species were compared as well as the lignin composition in different peat fractions, and their relation to source or decay was established.To determine whether the lignin parameters, derived from analysis of plants and peat fractions, can be used to reconstruct peat environment, they were applied to all 51 bulk peat samples of the upper meter of the Penido Vello core. The results show a strong effect of vegetation type and anaerobicity on generally-used lignin decomposition proxies, which indicates that such proxies are not reliable without information on the context.To examine the interaction between vegetation type and decomposition processes, the results of Sphagnum-dominated peat and graminoid-dominated peat were combined. In addition to the well-known pyrolytic marker from Sphagnum (4-isopropenylphenol), depth records of pyrolysis products specific for lichens and graminoids functioned well in both peatlands and are considered reliable markers for application in other peatlands. A number of other identified markers only functioned well within one of both peatlands. The different functioning of these markers in the two peatlands emphasises the importance of plant analysis prior to the use of pyrolytic biomarkers with low specificity, but also shows that supposedly non-specific pyrolysis products can be specific within a certain peatland ecosystem. The use of different peat fractions (NaOH-extractable and non-extractable peat) provided information on the degree of decomposition and allowed comparison with studies on peat humic acids and humin, and the generally applied colorimetric method to determine peat humification. Furthermore, the comparison of pyrolysates of extracts and residues for a selection of peat samples, in combination with factor analysis, allowed separation of the effects of source, and several stages of aerobic and anaerobic decay. Degradation of lignin-cellulose (vascular plants) and polyphenol-cellulose (Sphagnum) is discussed using the abundance of their markers (lignin moieties, levoglucosan and 4-isopropenylphenol) in pyrolysates of the different peat fractions, and gives insight into degradation mechanisms. The results indicated that, in Sphagnum litter, polyphenols are more easily degraded than polysaccharides. Comparison of pyrolysis results and C:N ratio showed that differences in litter quality between Sphagnum and vascular plants is a major factor that determines the variance of C:N with depth. Large part of the variation in C:N in Sphagnum-dominated peat is caused by decomposition rather than small increases of vascular plants upon drier conditions, while in graminoid-dominated peat this is not true and several processes may disturb the effect of mass loss on the C:N ratio. The C:N ratio can thus be a consistent decomposition proxy in Sphagnum-dominated peat but not in graminoid-dominated peat. Pyrolysis-GC/MS in combination with the applied research design provided detailed chemical information that gave insight in both vegetation and decomposition characteristics. This methodology thus has a high potential for the reconstruction of past environmental conditions.

Imperata grassland is a common vegetation type in Kalimantan (Indonesia), and other parts of South-East Asia. It indicates a high degree of degradation of the vegetation, and mostly occurs after slashing and burning of primary forest. Through secondary succession Imperata grassland is converted into new secondary forest and much of the original biodiversity is restored. The overall objective of the thesis was to study the regeneration of Imperata grasslands in East Kalimantan, and to measure the effects of regeneration on soil properties, with emphasis on the organic fraction. The research strategy was to compare plots of different regeneration stages, characterized by the period elapsed since the vegetation was last burned. Results show that during regeneration of Imperata grasslands, both vegetation composition and soil properties change, including chemistry of soil organic matter. Soil carbon stocks are higher under Imperata grasslands than under primary forest, and increase further upon natural regeneration of grassland to secondary forest. Highest carbon stocks are found in the later regeneration phases. Lower carbon stocks under primary forests are due to extremely low fertility, combined with shallow soils and low root mass in the topsoil. Root density as observed in the field is much higher under the grass vegetation. Results show as well that soil organic matter decomposition is most advanced under forest, as indicated by lower amounts of plant derived compounds and higher contribution of microbial matter. The results indicate that decomposition efficiency is related to soil organic matter chemistry, but more to abundance of N-compounds than to that of potentially recalcitrant compounds. In our case study, soil texture appears an important factor in the vegetation succession. On sandy soils, there is a strong increase with time of Pteridium aquilinum L., while the number of other species is lower. This slows down the development towards secondary forest. Canonical correspondence analysis (CCA) of environmental factors and vegetation show that pH, bulk density, sand and clay are the factors related to the distribution of species. The rapid secondary succession indicates that Imperata grasslands are not a final and stable stage of land degradation, but that frequent fires are necessary to maintain Imperata grasslands. If protected from fire and other intrusions such as shifting cultivation, Imperata grassland will readily develop into secondary forest. Imperata grasslands seem to be permanent because of human interference, especially through burning, and because so far few attempts have been made to sustainable rehabilitation.