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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.

Complexation of dissolved organic matter (DOM) with cations and minerals contributes to the stabilization of carbon in soils, and can enable the transport of metals in the environment. Hence, a proper understanding of mechanisms that control DOM binding properties in the soil is important for major environmental challenges, such as climate change and stream pollution. However, the role of DOM source in those mechanisms remains understudied. Here, we consider poorly drained tropical Podzols as a model environment to isolate effects of aluminium and DOM on sorption and desorption processes in podzolisation. We collected E- and Bh-horizons from a Brazilian coastal Podzol under tropical rainforest to conduct a column experiment, and percolated the columns with DOM collected from a stream (Stream), peat water (Peat), litter (Litter) and charred litter (Char). To quantify sorption and desorption from the columns, leachates were analysed for DOC content, aluminium content, pH, and the amount of fulvic acid relative to humic acid. The results showed large differences in DOC retention between DOM-types, which were consistent over all columns. Retention of DOC in the column varied between 25 % and 92 % for DOM-type Stream, between 33 % and 63 % for DOM-type Peat, between 22 % and 47 % for DOM-type Litter, and between 8 % and 49 % for DOM-type Char. Similarly, desorption from columns with B-horizon material highly differed between DOM-types. Percolation with DOM-types Stream and Peat caused a release of native DOC from B columns that was higher than in those percolated with water only. On the other hand, percolation of B columns with DOM-types Litter and Char caused a net DOC retention. These differences reflect that certain DOM-types hindered desorption, while other DOM-types caused active desorption. The large differences in sorption/desorption between DOM-types implies that changes in environmental conditions may highly influence the fate of soil carbon in Podzols.

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.

As the environment influences soil formation, loess–paleosols are important archives of former climatic conditions. However, this record is highly complex and all features need to be evaluated in order to obtain consistent information on soil formation. This study revises the pedological record of the Rocourt-paleosol complex, an important pedo-stratigraphic marker for the Eemian and Early Weichselian, at an exceptionally well-preserved in-situ sequence (Veldwezelt–Hezerwater, Belgian loess belt). Contrasting hypotheses exist considering the evolution of the parent material after the deposition of the Saalian loess and on the importance of aggrading aeolian deposition. In this study, soil morphological features and depth functions of X-ray diffraction, grain-size distribution, CEC, base saturation, total Fe, Al, K, Na and Ca content, pH and electrical conductivity were established to reconstruct deposition dynamics, weathering and carbonate content of the parent material. Texture analysis confirms the petrostratigraphic homogeneity of the parent material and suggests that it developed under a regime of fluctuating rates of primary dust deposition intermixed with periods of (fluvial) reworking of the dust. Strong weathering was identified in the lower stratigraphic unit, supporting the general consensus that it formed during the Eemian in Saalian loess. Less information is present to confirm the origin of the upper, less developed illuvial units, which may have formed by welding or by pedogenesis in locally redistributed or aeolian material. The overlying A-horizons are clearly less weathered, and evidence for early recalcification indicates that deposition of unweathered, calcareous sediments gained importance during the formation of these horizons.

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

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

To evaluate the effect of land use change on soil organic carbon, the carbon contents and stocks of primary forest, degraded pasture, and four improved pasture systems in Colombian Amazonia were compared in a flat and a sloping landscape. The improved pastures were Brachiaria humidicola , and Brachiaria decumbens , either in monoculture or in combination with native legumes. The age of the treatments was 30 years for degraded pasture and 10 or 15 years for each of the improved pastures. Carbon fractions were Total C, Oxidizable C, and Non-Oxidizable (stable) C. Stocks were compared using a fixed soil mass base. The degraded pasture in the flat landscape was abandoned and dominated by weeds, while that in the sloping area was overgrazed. The latter had much lower C stocks than the former. B. humidicola monoculture had the highest stocks both in flat and sloping areas, while the effect of the other three treatments varied. C replacement based on δ 13 C indicated that after 30 years, the degraded pasture still contained more than 50% forest-derived C in its topsoil. The fraction in the topsoil that is not replaced roughly coincides with the Stable C fraction. δ 13 C values suggest that the changes in carbon stocks ascribed to differences in land use may be – at least partially – inherited from the previous land use, thus confusing the interpretation of land use effects. Nevertheless, the introduction of improved pastures on degraded grassland is a feasible alternative of land use both for carbon sequestration and as an attractive economic alternative to farmers.

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

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

There is little information on the effects of land use change on soil Carbon stocks in Colombian Amazonia. Such information would be needed to assess the impact of this area on the global C cycle and the sustainability of agricultural systems that are replacing native forest. The aim of this study was to evaluate soil carbon stocks and changes after the clearing of the native forest, the establishment of pastures and the reclamation of the degraded pasture, in Caqueta, Colombia. We compared the contents of Total C, Oxidizable C and Non-Oxidizable (stable) C in four different land use systems, namely Monoculture ( Brachiaria grassland), Association ( Brachiaria + Arachis pintoi ), Forage Bank (a mixture of forage tree species), and Natural Regeneration of the pasture in both a flat area and a sloping one. The Degraded Pasture was the reference. Results showed that in the sloping area all treatments have higher Total Carbon stocks than the Degraded Pasture, while three of the treatments significantly increased the stocks of Non-Oxidizable C. In the flat landscape, only the Association significantly increased Total C stocks. Plowing and fertilization cause significant increases in Oxidizable carbon and decreases in Non-Oxidizable carbon. This effect needs further research, as C stability will influence equilibrium stocks. In the sloping area, improved pastures and fodder bank rapidly increased Total Carbon contents and stocks, with increases as large as10 ton.ha −1 yr −1 . In the Traditional Fodder Bank, which showed the largest increase, this is partially due to the application of organic manure. Surprisingly, also C stocks under Natural Regeneration were significantly higher than under the original Degraded Grassland. This increase was fully due to Non-Oxidizable Carbon, which is difficult to explain. Stable isotope analysis indicated that under improved grassland, especially Brachiaria monoculture, up to 40% of the original C in the upper 10 cm was replaced in 3.3 years.

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

Knowledge of the spatial distribution of total carbon is important for understanding the impact of regional land use change on the global carbon cycle. We studied spatial total carbon variability using transect sampling in an Imperata grassland area. Spatial variability was modeled following an isotropic stationary process with spherical and exponential variogram functions. Range and sill were estimated at 100 m and 82.29 ton2 ha-2, respectively. For nugget, sill ratio was estimated at 24%, implying a rather strong spatial dependence. In a subsequent total carbon stock inventory based on the sampling design mentioned above, we applied three types of estimators, namely, “naive average procedure,” “spatial average procedure,” and “spatial optimal procedure.” Estimation of total carbon stock (in ton ha-1) following naive average procedure (which erroneously ignores the spatial dependence) resulted in a considerably too narrow 95% confidence interval of 37.52 to 39.75, whereas the outcomes using spatial average procedure and spatial optimal procedure were 36.54 to 40.73 and 37.14 to 40.78), respectively, using the spherical model, and 36.63 to 40.64 and 37.07 to 40.64, respectively, using the exponential model. Our research indicated that, when total carbon stock estimation is the main goal, random sampling is optimal, whereas wide design sampling (i.e., shortest distance between sampling locations not less than the range) can be preferred in some cases

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

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

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

In the comparison of treatments in soil science experiments, a well-chosen experimental design is of crucial importance for making appropriate (optimal) statistical inference at low (lowest) costs. In the very common case that several observations from each plot are obtained, one should be aware that measurement units are not equivalent to so-called statistical experimental units. We illustrate the severe consequences of misinterpretations in some very commonly used experimental designs. Appropriate methodology is developed, which entails the aggregation of observations at the plot level based on the tools of spatial statistics, followed by a classical statistical analysis on the plot aggregated data. The model-based approach, in contrast to the design-based approach, appears to be a natural setting for comparison of treatments in soil-based experiments. Consequences for the planning of the experimental design are discussed, and recommendations are given

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

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

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

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

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

Soil characteristics in palaeosols are an important source of information on past climate and vegetation. Fingerprinting of soil organic matter (SOM) by pyrolysis-GC/MS is assessed as a proxy for palaeo-reconstruction in the complex of humic layers on top of the Rocourt pedosequence in the Veldwezelt-Hezerwater outcrop (Belgian loess belt). The fingerprints of the extractable SOM of different soil units are related to total organic carbon content, δ13C and grain-size analysis. Combined results indicate that the lower unit of the humic complex reflects a stable soil surface, allowing SOM build-up, intensive microbial activity and high decomposition. Higher in the profile, decomposition and microbial activity decrease. This is supported by a shift in the isotopic signal, an increasedUratio and evidence of wildfires. Although the chemical composition of the extracted SOM differed greatly from recent SOM, fingerprinting yielded detailed new information on SOM degree of decomposition and microbial contribution, allowing the reconstruction of palaeo-environmental conditions during pedogenesis.

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

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

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

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.

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

Peat domes in Kalimantan (Indonesia) are reported to loose their dome shape as a result of disturbance such as logging and artificial drainage. The loss of the dome shape can be caused by (a combination of) two major processes: compaction and oxidation. Because natural, undisturbed peat is a major sink for atmospheric CO2, the distinction between the two processes is of utmost importance with regard to carbon storage. In case of compaction, no CO2 need to be lost to the atmosphere. In case of oxidation, either as a result of increased decomposition upon improved drainage or by burning, all CO produced goes to the atmosphere. To estimate the contribution of oxidation and compaction to the loss of peat dome shape, research was conducted in the Mawas area in Central Kalimantan. Physical and chemical parameters of an intact and collapsed dome were compared. Increased bulk densities in the collapsed peat dome showed that considerable compaction has occurred. Depending on the initial bulk density, compaction has probably caused a subsidence from 2.2 to 4.0 in. According to ash content measurements, no significant oxidation has taken place, but increased EC found at the collapsed dome can be due to oxidation of at least 2.3 cur to 46.9 cm peat, which implies an emission of respectively 4.2 to 85.9 kg CO2 m(-2) over the 6 years since collapse. Compaction appeared to be a more important factor in the loss of dome structure than oxidation based on the estimated possible ranges in peat loss. Collapse of the dome had only minor influence on its chemical parameters. Regrowth did not seem to be hindered by the collapse and its consequences, but it was less at sites that had suffered recent fires. If peat growth resumes, collapse need not be detrimental to carbon storage. (c) 2006 Elsevier B.V. All rights reserved.

Kauri (Agathis australis) is generally associated with intense podzolisation, but little research has been carried out to substantiate this. We studied soil profiles, grain size distribution patterns and clay mineralogy under kauri and broadleaf/tree fern vegetation in the Waitakere Ranges, North Island, New Zealand. Kauri appears to cause increased breakdown of fines (0–10 μm) in the top of the profiles due to lower soil pH, relative to broadleaf/tree fern forest. The low soil pH under kauri apparently causes the loss of Al-hydroxy-interlayers from interlayered vermiculite and possibly the conversion of vermiculite to smectite. The effect of microtopographic differences in the landscape on the grain size distribution within the topmost horizons can be observed using laser grain size diffraction. Kauri does not cause podzolisation on andesitic material, and although similar weathering of clay minerals was observed, there was no evidence for transport of clay particles.

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

Tropical America (TA) holds 8% of the world's population, 11% of the world's continental area, 23% and 22%, respectively, of the world's forest and water resources, and 13% of the world's pasture and agro-pastoral land, this representing 77% of TA's agricultural land. Recent interest in carbon sequestration and preliminary research suggest that well-managed pasture systems in TA could provide a good combination of economic production, poverty reduction, recovery of degraded areas and delivery of environmental services, particularly, carbon sequestration. This paper presents 3-year research results generated by the "Carbon Sequestration Project, The Netherlands Cooperation CO-01002" on soil carbon stocks (SCS) for a range of pasture and silvo-pastoral systems prevalent in agro-ecosystems of TA compared to native forest and degraded land. In the tropical Andean hillsides, Colombia (1350-1900 m.a.s.l., 1800 mm rainfall/yr, 14-18°C mean annual temperature, medium to high slopes, medium fertility soils), SCS from Brachiaria decumbens pastures were statistically lower than those from native forest, but higher than those from natural regeneration of a degraded pasture (fallow land), degraded pasture and mixed-forage bank. In contrast, in the humid tropical forest of the Atlantic Coast, Costa Rica (200 m.a.s.l., 28-35°C, 3500 mm/year, poor acid soils), pasture or silvo-pastoral systems with native or planted pasture species such as Ischaemum ciliare, Brachiaria brizantha + Arachis pintoi and Acacia mangium + Arachis pintoi showed statistically higher SCS than native forest. Similar rankings were found in the humid tropical forest of Amazonia, Colombia (800 m.a.s.l., 30-42°C, 4200 mm/yr, flat, very poor acid soils) where improved Brachiaria pastures (monoculture and legume-associated) showed statistically higher SCS than native forest. In the sub-humid tropical forest of the Pacific Coast, Costa Rica (200 m.a.s.l., 6-month dry season, 2200 mm/year, poor acid soils) no statistical differences in SCS were found between land-use systems. In tropical ecosystems, improved pasture and silvo-pastoral systems show comparable or even higher SCS than those from native forests, depending on climatic and environmental conditions (altitude, temperature, precipitation, topography and soil), and represent attractive alternatives as C-improved systems.

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

The purpose of this study was to evaluate possible changes in soil organic matter (SOM) dynamics after establishing riparian forests on soils previously under Brazilian savannah ("cerrado"). We selected a site with a homogeneous Typic Aerie Red-Yellow Latosol (Anionic Acrustox). Part of this site was maintained under native vegetation (grassy cerrado C-4-dominated), and part was planted with riparian species (C-3) in 1992. Litter and soil samples were collected and analysed (total organic carbon, total nitrogen, delta(13)C isotopic analysis, and SOM density fractionation). Due to the predominance of grasses, carbon input was mainly below ground in cerrado. In such a soil, the decomposition process was more efficient, and much C and N were transferred to the heavy fraction. When forest was planted, there was a change from belowground to aboveground litter input (largely superficial), leading to higher C and N stocks in the light and lower stocks in the heavy fraction (resulting in lower stocks for bulk soil). The introduction of the C-3 vegetation decreased the soil delta(13)C signature. It has occurred particularly in the topsoil (0 - 5 cm) due to the deposition of C-3 litter on the soil surface. At the same time, the presence of cerrado-remaining C below 5 cm maintained higher delta(13)C values in this layer. During the 8 years after forest plantation, the input mode influenced both the delta(13)C distribution with depth, and the C replacement: between 0 and 2.5 cm, nearly 50% of cerrado-derived C was replaced by forest-derived C, while below 5 cm, replacement was around 20%. The relatively rapid C dynamics in this Oxisol (27% replacement in the top 20 cm after 8 years of forest plantation) shows that, under tropical conditions, significant changes may occur in a short period of time. (C) 2004 Elsevier B.V. All rights reserved.

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.