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European and Flemish climate-change policies aim to enhance carbon (C) storage in soils of conservation areas, including natural areas such as forests, grasslands and wetlands. Soil capability and condition however may impact C persistence and material cycles in soils, and therefore the sustainability of this policy effort, by making soil C stocks more vulnerable to climatic anomalies, shocks and disturbances. Edaphic limitations in terms of nutrients, acidity, temperature or moisture availability have been shown to affect soil C persistence, but processes behind this effect remain elusive and poorly quantified.In this contribution, we therefore present several case studies in western European forests and wetlands, where we assess how the molecular composition of several soil organic matter fractions varies along gradients of soil cover, edaphic conditions and perturbation intensity. Furthermore, by comparing different fractions and markers, we evaluate the suitability of different methods to evaluate changes in soil carbon dynamics, as a tool to predict the potential impact of anthropogenic stresses and management interventions on soil carbon persistence.

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.

The molecular composition of soil organic matter (SOM) contains key information on the persistence of soil carbon (C) in relation to changes in vegetation and environmental factors. Depending on the ecosystem, analytical method and specific objectives, many SOM fractions and numerous fractionation schemes have been proposed to study soil C. However, the molecular composition and environmental significance of those different SOM fractions have not yet been compared systematically. We use a reverse fit approach to fill this knowledge gap: i.e. we chose a study area with a well-known land history to assess which information is stored in the most frequently analysed SOM fractions. The Gaume forest (Belgium) is an ancient deciduous forest (>200 years) in which small stands were converted to Norway spruce (Picea abies) 40–50 years ago. Those stands are located along a lithological gradient in soil buffering capacity. We investigated the molecular composition of bulk mineral soil samples and five organic SOM fractions by pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). The SOM fractions included particulate OM (POM), water extractable OM (WEOM), and fractions obtained by alkaline extraction, including the traditionally used humic acid (HA) and fulvic acid (FA) and the total base extract from which they are obtained (BE). Our results indicate that pyrolysates of bulk mineral soil did not prove useful to reflect environmental changes after forest stand conversion. Principal Component Analysis indicated that within each organic fraction similar changes occurred when comparing soil depths, degree of SOM decomposition, litter inputs, and soil buffering capacity. However, only the HA and BE appeared successful in capturing all these processes: the degree of SOM decomposition was not expressed in pyrolysates from the POM, differences in litter input between forest stand types were not evidenced in the WEOM, and effects of buffering capacity were not demonstrated in the WEOM and FA fractions. Thus, the molecular composition of different SOM fractions can be used complementary to each other to study environmental and ecological effects of forest stand conversion on soil C dynamics. ispartof: Geoderma vol:430 status: Published online

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.

Soil organic matter (SOM) plays an important role not only for agriculture but also in the global carbon (C) balance with a potential to mitigate climate change. Land-use changes from native vegetation to intensive agricultural use enhance mineralization of SOM and thereby cause decreases in the amount of soil C. Association of SOM on soil minerals is highlighted as key stabilization mechanism of SOM. To examine the contribution of land-use change and soil mineralogy on soil C losses, soils with different soil mineralogy assemblage were studied from four areas in Brazil, all having sites with agriculture and nearby soils under native vegetation. We assessed SOM stability by thermogravimetric (TGA) and differential scanning calorimetry (DSC) and the molecular composition of functional soil C pools by pyrolysis gas chromatography/mass spectrometry (Py–GC/MS). On average, 33 % of soil C was lost in three sites after land-use change. Py-GC/MS indicates a dominance of reworked and/or microbial material (58–99 % N-containing products and carbohydrates), and low contribution from plant-derived products such as lignin phenols (from 0.1 to 7.7 %), and striking similarities in molecular composition between native vegetation and corresponding sites under agriculture. Thermal data indicate lower energy content in soils under native vegetation than agriculture, confirming microbial-derived SOM. The gibbsite content was positively correlated to N-containing products in both SOM extracted by alkaline solution (r2 = 0.60) and SOM residual after alkaline extraction (r2 = 0.82), while the kaolinite content showed a negative correlation with N-containing compounds (r2 = 0.72) and a positive one with carbohydrates (r2 = 0.48). Thus although SOM content highly decreased upon horticulture, both Py-GC/MS and thermal analyses indicate that SOM composition is mainly controlled by site instead of land-use, and the strong correlations with clay minerals suggest a mineralogical control on SOM composition.

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.

Peatlands, storing significant amounts of carbon, are extremely vulnerable to climate change. The effects of climate change are projected to lead to a vegetation shift from Sphagnum mosses to sedges and shrubs. Impacts on the present moss-dominated peat remain largely unknown. In this study, we used a multiproxy approach to investigate the influence of contrasting vascular plant types (sedges, shrubs) on peat chemistry and decomposition. Peat cores of 20 cm depth and plant material (Sphagnum spp., Calluna vulgaris and Eriophorum vaginatum) from two ombrotrophic peatlands in the Italian Alps with a mean annual temperature difference of 1.4 ∘C were analyzed. Peat cores were taken under adjacent shrub and sedge plants growing at the same height above the water table. We used carbon, nitrogen and their stable isotopes to assess general patterns in the degree of decomposition across sampling locations and depths. In addition, analytical pyrolysis was applied to disentangle effects of vascular plants (sedge, shrub) on chemical properties and decomposition of the moss-dominated peat. Pyrolysis data confirmed that Sphagnum moss dominated the present peat irrespective of depth. Nevertheless, vascular plants contributed to peat properties as revealed by, e.g., pyrolysis products of lignin. The degree of peat decomposition increased with depth as shown by, e.g., decreasing amounts of the pyrolysis product of sphagnum acid and increasing δ13C with depth. Multiple parameters also revealed a higher degree of decomposition of Sphagnum-dominated peat collected under sedges than under shrubs, particularly at the high temperature site. Surprisingly, temperature effects on peat decomposition were less pronounced than those of sedges. Our results imply that vascular plants affect the decomposition of the existing peat formed by Sphagnum, particularly at elevated temperature. These results suggest that changes in plant functional types may have a stronger impact on the soil carbon feedback in a warmer world than hitherto assumed.

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 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.

Glycerol dialkyl glycerol tetraethers (GDGTs) are membrane-spanning lipids from Bacteria and Archaea that are ubiquitous in a range of natural archives and especially abundant in peat. Previous work demonstrated that the distribution of bacterial branched GDGTs (brGDGTs) in mineral soils is correlated to environmental factors such as mean annual air temperature (MAAT) and soil pH. However, the influence of these parameters on brGDGT distributions in peat is largely unknown. Here we investigate the distribution of brGDGTs in 470 samples from 96 peatlands around the world with a broad mean annual air temperature (-8 to 27 degrees C) and pH (3-8) range and present the first peat-specific brGDGT-based temperature and pH calibrations. Our results demonstrate that the degree of cyclisation of brGDGTs in peat is positively correlated with pH, pH = 2.49 x CBTpeat + 8.07 (n = 51, R-2 = 0.58, RMSE = 0.8) and the degree of methylation of brGDGTs is positively correlated with MAAT, MAAT(peat) (degrees C) = 52.18 x MBT'(5me) - 23.05 (n = 96, R-2 = 0.76, RMSE = 4.7 degrees C). These peat-specific calibrations are distinct from the available mineral soil calibrations. In light of the error in the temperature calibration (similar to 4.7 degrees C), we urge caution in any application to reconstruct late Holocene climate variability, where the climatic signals are relatively small, and the duration of excursions could be brief. Instead, these proxies are well-suited to reconstruct large amplitude, longer-term shifts in climate such as deglacial transitions. Indeed, when applied to a peat deposit spanning the late glacial period (similar to 15.2 kyr), we demonstrate that MAAT(peat) yields absolute temperatures and relative temperature changes that are consistent with those from other proxies. In addition, the application of MAAT(peat) to fossil peat (i.e. lignites) has the potential to reconstruct terrestrial climate during the Cenozoic. We conclude that there is clear potential to use brGDGTs in peats and lignites to reconstruct past terrestrial climate. (C) 2017 The Authors. Published by Elsevier Ltd.

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.

The effect of long term degradation on soil black carbon (BC) is important for correctly interpreting the role of BC in the global carbon cycle and in biochar studies. To address this, we studied three soil profiles (0–2 m depth, > 9000 yr) in undisturbed Brazilian Cerrado vegetation naturally affected by wildfires. The molecular composition of several soil organic matter (OM) pools was studied using analytical pyrolysis. Other analyses included general chemical and physical characteristics and micromorphology. The soil OM fractions included the free light fraction (FLF; particulate OM), the occluded light fraction (OLF; particulate OM within aggregates), the 0.1 M NaOH extractable OM (EXT; comparable with the combined humic acid and fulvic acid fractions) and the remaining residue (RES; treated with HF/HCl; comparable with the humin fraction). Although each fraction represents a continuum of material, they were assigned a different degradation level. The light fractions represent relatively intact BC (i.e. charcoal) of which the OLF is more degraded than the FLF, the EXT contains more decomposed material and the RES represents residual OM that is difficult to decompose. The largest contribution to the total soil OM was from RES and EXT, together accounting for > 80% of the total soil C. The relative contribution from BC-associated pyrolysis products was generally large for all fractions (between 5% and 57%) and showed an increase with depth in the OLF and RES. Based on factor analysis exclusively applied to BC-associated pyrolysis products from all four OM fractions, two BC degradation indices were extracted: Index 1, reflecting depolymerization and relative enrichment of N, and Index 2, reflecting a relative increase in condensed structures. Both indices gradually increased with depth for all fractions, except FLF. Based on these indices, we selected some simple ratios that showed good correlation with them (r2 > 0.7). For Index 1, reflecting depolymerization, adequate ratios for all fractions included benzene/indene and benzene/C1 naphthalenes. For Index 2, reflecting the relative accumulation of condensed BC, adequate ratios for all fractions included biphenyl/C2-benzene, fluorene/C2-benzene and 4-ring PAHs/C2-benzene.

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.

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.

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.

Contiene 6 figuras, 2 tablas., Posidonia oceanica forms extensive peat-like deposits (mats) in Mediterranean coastal waters, which have a potential as carbon sinks and archives of environmental change. Nonetheless, the organic chemistry of both P. oceanica plant materials, as well as the environmental and diagenetic effects on the composition of its detritus, is poorly understood. We analyzed plant organs of P. oceanica and the coarse organic matter from a mat core spanning 750 yrs using pyrolysis techniques (PY-GC-MS and THM-GC-MS) to improve our understanding of their molecular properties and their preservation upon mat development. It appeared that leaf sheaths, roots and the outer parts of rhizomes were composed predominantly of phenolic constituents based on p-hydroxybenzoic acid (p-HBA), which is atypical for vascular plants, in addition to carbohydrates and lignin. The inner rhizome and leaf blades had a different composition, with predominance of carbohydrates. The seagrass detritus in the mat was composed mainly of p-HBA phenolic material and carbohydrates, confirming earlier studies showing that the coarse detritus in the mat originates largely from Posidonia sheath, root and rhizome debris. The intermolecular arrangement of the p-HBA remains unclear, as they seem to correspond to ester-bound phenols yet their persistence in the mat attributes them a refractory nature. Variations in molecular composition within the mat are probably associated with diagenetic alteration of P. oceanica detritus, such as the decomposition of minor amounts of fatty acids, chlorophyll and syringyl lignin, and selective preservation of p-HBA relative to carbohydrates. This work lays the foundations for a molecular understanding of carbon storage within the mats and the environmental changes recorded therein., The pyrolysis experiments and J.K. were funded by the project CGL2010-20662 (Plan Nacional de I+D+i, Ministerio de Economía y Competitividad, España) and grant GPC2014/009 (Xunta de Galicia). O.S. was supported by the ECU Faculty Research Grant Scheme and the CSIRO Flagship Marine & Coastal Carbon Biogeochemical Cluster (Coastal Carbon Cluster). The field work and sample preparation were funded by the SUMILEN project “Advances in sampling techniques, biogeochemical characterization, and quantification of the millenary deposits of seagrasses” (Plan Estatal CTM2013- 47728-R) and PALEOPARK project “Millenary changes in the insular Spanish National Parks: perturbations, resilience and trends after the seagrass archives” (Parques Nacionales 1104/2014). This is a publication of the Group of Benthic Ecology 2014 SGR 120.

The soils in the NE of the Magdalena province (Colombia) are subject to intense degradation primarily because of the low accumulation rate of soil organic matter (SOM) and its fast turnover. Numerous traditional studies have aimed to mitigate this situation, focusing on the analysis of total SOM contents. The present study aimed to determine SOM quality from six areas under humid and dry tropical forest with different pedoclimatic conditions, using molecular characterization. For each area, sites with different current land use were studied, including forest and cultivated sites. We applied analytical pyrolysis (pyrolysis-GC/MS) to aqueous NaOH-extractable SOM from surface soil samples. One-hundred and ten pyrolysis products were identified and quantified, from the following chemical groups: N-containing compounds (34.1 ± 5.1%), carbohydrate markers (21.1% ± 7.1%), monocyclic aromatic compounds (20.0% ± 4.5%), aliphatic compounds (7.7% ± 1.4%), phenols (7.0% ± 5.0%), polycyclic aromatic compounds (3.6% ± 0.9 %), lignin products (0.3% ± 0.3%) and other compounds (0.2% ± 0.1%). SOM of all studied areas showed a large proportion of N-containing products, indicating a high contribution from microbial material to the SOM. Multivariate statistics allowed for the differentiation between microbial-derived and plant-derived SOM (Factor 1) and the relative proportion of burning residues (Factor 2), and indicated that pedoclimatic conditions exert more influence on SOM composition (cool and humid zones were enriched in microbial SOM while dry zones contained more plant-derived SOM) than land use for the studied soils.

Replacing pastures (PA) with sugarcane (SG) has been deemed an agronomically feasible strategy for sugarcane expansion in Brazil. However, there are some uncertainties about the environmental impacts regarding this land use change (LUC), mainly related to soil organic matter (SOM), a key factor of environmental sustainability of Brazilian ethanol. LUC-related losses of SOM can overcome the C savings from biofuels. The molecular composition of SOM was evaluated to understand the C dynamics regarding LUC from PA to SG, using native vegetation (NV) as reference. Our study area was located in the south-central region of Brazil. Soil sampling was performed at three depths (0-0.1m, 0.2-0.3m and 0.9-1m) in three representative sites with known LUC history and management practice since 1970. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was chosen to study SOM chemistry. Content and isotopic composition of soil organic C and N were also determined. The LUC caused decreases on C and N contents and on δ(13)C isotopic values. Depth was the major factor that influenced SOM composition, while the influence of LUC was mainly evident in surface soils and diminished rapidly with depth. The main difference in SOM composition undergoing the conversion PA-SG was a higher contribution from compounds associated to fresh litter inputs. The high contribution from fresh litter, having a relatively low mean residence time and increasing decomposition rates, is probably a major factor that drives C losses in areas undergoing sugarcane expansion.

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.

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.

We present a multiproxy characterization of a complex, polycyclic soil sequence from Les Alcusses, Moixent(Valencia, SE Spain). The area has abundant settlements dating from early Neolithic to Roman times. The sequence comprises six main units, dating back to 8.7-8.5kacalBP. We integrated mineralogy, inorganic (pH, grain size, elemental composition) and organic chemistry (pyrolysis gas chromatography/mass spectrometry, pyrolysis-GC/MS), micro-charcoal, pollen and non-pollen palynomorph (NPP) data. All data is contextualized within a framework of archaeological information and radiocarbon dating, with the aim of deciphering the Holocene environmental changes.We infer a shift from wetter and warmer, in the early-mid Holocene, to drier and cooler climatic conditions with increased fire occurrence, in the mid-late Holocene (particularly after 5.3kacalBP). Although the pollen record indicates a rapid forest retreat and expansion of grasslands for the Neolithic period, local proxies (molecular soil OM indicators and NPP) point to the presence of pine forest in the studied location well after the regional decline started. The same proxies suggest a sharp forest decline after about 7.0kacalBP. Strong soil erosion, likely linked both to climatic instability and the intensification of human exploitation, resulted in a hiatus from the late Neolithic to the Roman period. A certain climate amelioration, wetter conditions and land abandonment or, at least, lower human pressure, are suggested for the late Roman period/Early Middle Ages. Direct evidence of changes in soil properties due to agriculture was not detected in the sequence except for the upper soil unit studied, which reflects intense agricultural management (with the possible use of agrochemicals). © 2014 Elsevier Ltd., This study was funded by the European Research Council (Advanced Grant No. 2305619, project ‘AGRIWESTMED: Origins and spread of agriculture in the western Mediterranean region’) and the Diputación de Valencia-Museo de Prehistoria de Valencia (2009/CI585). Daniel Abel Schaad and Judith Schellekens were supported by AGRIWESTMED project.

Tropical climate dynamics play a major role in the global climate system. Precipitation patterns in the Serra do Espinhaco Meridional (Minas Gerais, Brazil) are influenced by both the South Atlantic Convergence Zone (SACZ) and the Inter Tropical Convergence Zone (ITCZ). This makes the area important for the interpretation of climate dynamics. The composition of the Holocene Pau de Fruta peat deposit was analysed using pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS). Molecular records agreed well with δ13C and δ15N stable isotopes, C content and mineral content, and pollen records. Changes in peatland plant species composition and fire occurrence indicated several wet and dry periods for the Pau de Fruta peatland during the Holocene; from the beginning of the Holocene to 7400 cal yr BP (phase I; dry and cold), from 7400 to 4200 cal yr BP (phase II; wet and warm), from 4200 to 1000 cal yr BP (phase III; dry and warm), from 1000 to 400 cal yrBP (phase IV; wet and warm) and from 400 cal yr BP to the present (V). The hydrological shifts showed a chronology comparable with that described in other palaeoclimatic studies for central-eastern Brazil, indicating that local conditions agree with regional ones. Analytical Py of the peat deposit provided a multi-proxy record via the identification of specific markers for both peatland plants (vegetation) and charred material (fire), whereas the general chemistry provided information on the degree of decomposition of the organic matter. Molecular chemistry of the peat core sampled at high resolution provided insight into peatland C dynamics, which is important for the interpretation of C sequestration in tropical peatlands. Molecular aspects accurately reflected local environmental change. The general agreement of Py data with pollen and inorganic chemistry supports the use of the molecular approach, because it provides local proxy indicators for peatlands, avoiding a mixture of local and regional signals.

Peat humification or decomposition is a frequently used proxy to extract past time changes in hydrology and climate from peat bogs. During the past century several methods to determine changes in peat decomposition have been introduced. Most of these methods are operationally defined only and the chemical changes underlying the decomposition process are often poorly understood and lack validation. Owing to the chemically undefined nature of many humification analyses the comparison of results obtained by different methods is difficult. In this study we compared changes in peat decomposition proxies in cores of two peat bogs (Königsmoor, KK; Kleines Rotes Bruch, KRB) from the Harz Mountains (Germany) using C / N ratios, Fourier transform infrared spectra absorption (FTIR) intensities, Rock Eva® oxygen and hydrogen indices, δ13C and δ15N isotopic signatures and UV-absorption (UV-ABS) of NaOH peat extracts. In order to explain parallels and discrepancies between these methods, one of the cores was additionally analysed by pyrolysis gas chromatography mass spectrometry (pyrolysis-GC-MS). Pyrolysis-GC-MS data provide detailed information on a molecular level, which allows differentiation of both changes attributed to decomposition processes and changes in vegetation. Principal component analysis was used to identify and separate the effects of changes in vegetation pattern and decomposition processes because both may occur simultaneously upon changes in bog hydrology. Records of decomposition proxies show similar historical development at both sites, indicating external forcing such as climate as controlling the process. All decomposition proxies except UV-ABS and δ15N isotopes show similar patterns in their records and reflect to different extents signals of decomposition. The molecular composition of the KK core reveals that these changes are mainly attributed to decomposition processes and to a lesser extent to changes in vegetation. Changes in the molecular composition indicate that peat decomposition in the KK bog is mainly characterized by preferential decomposition of phenols and polysaccharides and relative enrichment of aliphatics during drier periods. Enrichment of lignin and other aromatics during decomposition was also observed but showed less variation than polysaccharides or aliphatics, and presumably reflects changes in vegetation associated with changes in hydrology of the bogs. Significant correlations with polysaccharide and aliphatic pyrolysis products were found for C / N ratios, FTIR-band intensities and for hydrogen index values, supporting that these decomposition indices provide reasonable information. Correlations of polysaccharide and aliphatic pyrolysis products with oxygen index values and δ13C was weaker, assumingly indicating carboxylation of the peat during drier periods and enrichment of isotopically lighter peat components during decomposition, respectively. FTIR, C / N ratio, pyrolysis-GC-MS analyses and Rock Eval hydrogen indices appear to reflect mass loss and related changes in the molecular peat composition during mineralization best. Pyrolysis-GC-MS allows disentangling the decomposition processes and vegetation changes. UV-ABS measurements of alkaline peat extracts show only weak correlation with other decomposition proxies and pyrolysis results as they mainly reflect the formation of humic acids through humification and to a lesser extent mass loss during mineralization.

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

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

Some well-drained podzols on quartz sands in the Netherlands and neighbouring Belgium and Germany show mottling in all horizons due to selective removal of organic matter. Phospholipid analysis and morphology of the mottles suggests that this removal is due to a combination of bacteria, fungi, and actinomycetes. Investigation by pyrolysis-GC/MS of organic matter in the depleted zones as compared to their surroundings indicates (1) selective decay of relatively palatable components, (2) residual accumulation of aliphatic biopolymers such as cutan and suberan that produce alkanes, alkenes and methylketones upon pyrolysis, and (3) accumulation of microbial polysaccharides and N-containing compounds. Although the selective organic matter decay in the depleted mottles is similar to the process that causes degradation of organic matter at the top of the B-horizon and its conversion to an E-horizon, the essential difference is that, while decay at the E–B-horizon transition in podzols is governed by the presence or absence of aluminium and iron, the micro flora that is responsible for the decay mottles acts independently from metal concentrations.

Methane emissions from peatlands contribute significantly to atmospheric CH4 levels and play an essential role in the global carbon cycle. The stable carbon isotopic composition (δ13C) of bacterial and plant lipids has been used to study modern and past peatland biogeochemistry, especially methane cycling. However, the small number of recent peatlands that have been characterised and the lack of consistency between target compounds means that this approach lacks a rigorous framework. Here, we undertake a survey of bacterial and plant lipid δ13C values in peatlands from different geographic regions, spanning a wide range of temperature (−8 to 27 °C) and pH (∼3 to 8), to generate a reference dataset and probe drivers of isotopic variability. Within our dataset, the carbon fixation pathway predominantly determines leaf wax (n-alkane) δ13C values. Bacterial-derived C31 hopane δ13C values track those of leaf waxes but are relatively enriched (0 to 10‰), indicating a heterotrophic ecology and preferential consumption of 13C-enriched substrates (e.g. carbohydrates). In contrast, ≤C30 hopanoids can be strongly 13C-depleted and indicate the incorporation of isotopically light methane into the bacterial community, especially at near neutral pH (∼5–6 pH). Previous analysis of Eocene sediments has suggested isotopic decoupling between C31 and ≤C30 hopanoid δ13C values. Our work suggests a globally widespread decoupling in recent peatlands; this persists despite the profound diversity of hopanoid producing bacteria and associated controls on their δ13C values and it has significant implications for future work. Re-analysis of published data from: (1) the (mid-to-early) Holocene and late Glacial, and (2) latest Paleocene and earliest Eocene in this revised context highlights that perturbations to the peatland methane cycle occurred during the past, and we envisage that this approach could provide unique (qualitative) insights into methane cycling dynamics throughout the geological record.

Evidências arqueológicas indicam que as atividades humanas antigas nos habitats amazônicos transformaram significativamente a paisagem na vizinhança dos assentamentos. Um registro marcante são os solos afetados pelo homem pré-histórico e que apresentam cor escura, restos de material arqueológico (fragmentos cerâmicos e de artefatos líticos), fragmentos de carvão vegetal e alta fertilidade. O Sítio Porto Santarém, localizado a margem do rio Tapajós, possui todas as evidências desta ocupação e, por isso, foi escolhido como o objeto deste estudo. O objetivo aqui proposto consiste correlacionar os diferentes métodos analíticos e de interpretação (biológicos, isotópicos, moleculares e de imagem) para compreender os fatores de formação da Terra Preta no Sítio PA-ST-32. Os resultados indicaram um predomínio de cobertura florestal (C3) em todas as escavações durante a faixa de tempo abordada (400±30 a 3.830±30 anos AP), com enriquecimento isotópico em profundidade, como resultado, provavelmente, da dieta dos indígenas. Também, verificou-se um teor maior de carbono na TPI em relação ao perfil sem a camada antrópica, mas que mostraram valores similares (TIC%) de poliaromáticos oriundos da queima (carvão pirogênico). Foram identificados 100 fragmentos de carvão, onde 62% pertencem aos gêneros representativos da família Fabaceae. Archaeological evidence indicates that ancient human activities in Amazonian habitats have significantly transformed the landscape in the vicinity of the settlements. A striking record are the soils affected by prehistoric man and which are dark in color, remains of archaeological material (ceramic fragments and lytic artifacts), fragments of charcoal and high fertility. The Porto Santarém Site, located on the banks of the Tapajós River, has all the evidence of this occupation and, therefore, was chosen as the object of this study. The objective here is to correlate the different analytical and interpretation methods (biological, isotopic, molecular and image) to understand the formation factors of Black Earth in the PA-ST-32 site. The results indicated a predominance of forest cover (C3) in all excavations during the time range (400 ± 30 to 3,830 ± 30 years BP), with deep isotopic enrichment, probably as a result of indigenous diet. Also, a higher carbon content was observed in TPI in relation to the profile without the anthropic layer, but they showed similar values (TIC%) of polyaromatics from the burning (pyrogenic charcoal). 100 charcoals fragments were identified, where 62% belong to the representative genus of the Fabaceae family.

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.