Investigation on the Stabilization of the Humus in Mollisols

Soil organic matter in Mollisols is often preserved for an extremely long period (e.g. > 3000 years). We confirmed that the stable organic matter in Mollisols is the medium to coarse sized (0.2–2.0 μm) clay-humus complex with humic acid combined with calcium as the main organic constituent. The argillic horizon contained relatively large amounts of clay-humus complexes and had relatively high carbon contents, humic acid/fulvic acid ratios and degrees of humification of humic acid. Medium clay and coarse clay fractions preserved the organic carbon most efficiently. Highly humified humic acid could be detected even in the uppermost part of the Ah horizon and was probably stabilized in lower horizons by forming a complex with clay fractions.     

Total and carboxyl acidity and methoxyl groups of humic acid preparations of chernozemic soils

Abstract

Alkaline‐soluble, acid‐precipitable organic matter from the Ah and Bm horizons of Chernozemic soils developed on four parent materials in each of three soil zones was analyzed for total and carboxyl acidity, and methoxyl groups. The values are expressed as meq/g dry ash‐free organic matter.

Total acidity generally was higher in the Black Chernozems than in the Brown Chernozems and higher in the Bm horizon than in the Ah horizon. The distribution of carboxyl acidity between the Ah and companion Bm horizons of individual soils appeared to be related to texture and rainfall.

The. methoxyl group content of the Brown Chernozems was larger than that of the .Dark Brown Chernozems, which in turn had a larger methoxyl group content than that of the Black Chernozems. It was concluded that the organic matter in the Ah horizons of the Brown Chernozems was not as humified as that of the Black Chernozems. The pH value and a minimum clay content are possible determining factors as to the amounts of methoxyl carbon present.     

Soil organic matter stabilization in acidic forest soils is preferential and soil type-specific

Minerals with large specific surface areas promote the stabilization of soil organic matter (SOM). We analysed three acidic soils (dystric, skeletic Leptic Cambisol; dystric, laxic Leptic Cambisol; skeletic Leptic Entic Podzol) under Norway spruce (Picea abies) forest with different mineral compositions to determine the effects of soil type on carbon (C) stabilization in soil. The relationship between the amount and chemical composition of soil organic matter (SOM), clay content, oxalate‐extractable Fe and Al (Fe_o; Al_o), and dithionite‐extractable Fe (Fe_d) before and after treatment with 10% hydrofluoric acid (HF) in topsoil and subsoil horizons was analysed. Radiocarbon age, ¹³C CPMAS NMR spectra, lignin phenol content and neutral sugar content in the soils before and after HF‐treatment were determined and compared for bulk soil samples and particle size separates. Changes in the chemical composition of SOM after HF‐treatment were small for the A‐horizons. In contrast, for B‐horizons, HF‐soluble (mineral‐associated) and HF‐resistant (non‐mineral‐associated) SOM showed systematic differences in functional C groups. The non‐mineral associated SOM in the B‐horizons was significantly depleted in microbially‐derived sugars, and the contribution of O/N‐alkyl C to total organic C was less after HF‐treatment. The radiocarbon age of the mineral‐associated SOM was younger than that of the HF‐resistant SOM in subsoil horizons with small amounts of oxalate‐extractable Al and Fe. However, in horizons with large amounts of oxalate‐extractable Al and Fe the HF‐soluble SOM was considerably older than the HF‐resistant SOM. In acid subsoils a specific fraction of the organic C pool (O/N‐alkyl C; microbially‐derived sugars) is preferentially stabilized by association with Fe and Al minerals. Stabilization of SOM with the mineral matrix in soils with large amounts of oxalate‐extractable Al_o and Fe_o results in a particularly stable and relatively old C pool, which is potentially stable for thousands of years.     

Fixation of radiocaesium in an acid brown forest soil

The OAh and Ah horizons of acid brown and podzolic forest soils are reported to fix more radiocaesium than the mineral B horizons beneath them. We determined the respective influence of organic matter and clay minerals on the magnitude of Cs⁺ retention in a strongly acid brown forest soil in Belgium. The soil contained mica throughout the profile. Vermiculite was identified in the OAh and Ah horizons, and hydroxy interlayered vermiculite (HIV) in the Bw horizon. The OAh and Ah clay fraction retained much more Cs⁺ than the Bw horizon. The extraction of Al interlayers by Na-citrate resulted in a marked increase in Cs⁺ fixation in the Bw clays as well as the collapse of the vermiculitic layers after K⁺ saturation. Organic matter had a strong but indirect effect on Cs⁺ fixation. In the Bw horizon, acid weathering of layer silicates releases free Al and produces HIV minerals in which Al polymers block the access of radiocaesium onto Cs⁺-specific sites. In OAh and Ah horizons, free Al is complexed by organic acids. Consequently, the interlayer specific sites remain accessible for Cs⁺ fixation.     

Location and chemical composition of stabilized organic carbon in topsoil and subsoil horizons of two acid forest soils

The ¹⁴C age of soil organic matter is known to increase with soil depth. Therefore, the aim of this study was to examine the stabilization of carbon compounds in the entire soil profile using particle size fractionation to distinguish SOM pools with different turnover rates. Samples were taken from a Dystric Cambisol and a Haplic Podzol under forest, which are representative soil types under humid climate conditions. The conceptual approach included the analyses of particle size fractions of all mineral soil horizons for elemental composition and chemical structure of the organic matter by ¹³C cross-polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy. The contribution of phenols and hydroxyalkanoic acids, which represent recalcitrant plant litter compounds, was analyzed after CuO oxidation.In the Dystric Cambisol, the highest carbon concentration as well as the highest percentage of total organic carbon are found in the <6.3 μm fractions of the B and C horizons. In the Haplic Podzol, carbon distribution among the particle size fractions of the Bh and Bvs horizons is influenced by the adsorption of dissolved organic matter. A relationship between the carbon enrichment in fractions <6.3 μm and the ¹⁴C activity of the bulk soil indicates that stabilization of SOM occurs in fine particle size fractions of both soils. ¹³C CPMAS NMR spectroscopy shows that a high concentration of alkyl carbon is present in the fine particle size fractions of the B horizons of the Dystric Cambisol. Decreasing contribution of O-alkyl and aromatic carbon with particle size as well as soil depth indicates that these compounds are not stabilized in the Dystric Cambisol. These results are in accordance with data obtained by wet chemical analyses showing that cutin/suberin-derived hydroxyalkanoic acids are preserved in the fine particle size fractions of the B horizons. The organic matter composition in particle size fractions of the top- and subsoil horizons of the Haplic Podzol shows that this soil is acting like a chromatographic system preserving insoluble alkyl carbon in the fine particle size fractions of the A horizon. Small molecules, most probably organic acids, dominate in the fine particle size fractions of the C horizons, where they are stabilized in clay-sized fractions most likely due to the interaction with the mineral phase. The characterization of lignin-derived phenols indicated, in accordance with the NMR measurements, that these compounds are not stabilized in the mineral soil horizons.     

Organic matter quality of a forest soil subjected to repeated drying and different re‐wetting intensities

Extended drought periods followed by heavy rainfall may increase in many regions of the Earth, but the consequences for the quality of soil organic matter and soil microbial communities are poorly understood. Here, we investigated the effect of repeated drying and re‐wetting on microbial communities and the quality of particulate and dissolved organic matter in a Haplic Podzol from a Norway spruce stand. After air‐drying, undisturbed soil columns were re‐wetted at different intensities (8, 20 and 50 mm per day) and time intervals, so that all treatments received the same amount of water per cycle (100 mm). After the third cycle, SOM pools of the treatments were compared with those of non‐dried control columns. Lignin phenols were not systematically affected in the O horizons by the treatments whereas fewer lignin phenols were found in the A horizon of the 20‐ and 50‐mm treatments. Microbial biomass and the ratio of fungi to bacteria were generally not altered, suggesting that most soil microorganisms were well adapted to drying and re‐wetting in this soil. However, gram‐positive bacteria and actinomycetes were reduced whereas gram‐negative bacteria and protozoa were stimulated by the treatments. The increase in the (cy 17: 0 + cy 19: 0)/(16:1ω7c + 18:1ω7c) ratio indicates physiological or nutritional stress for the bacterial communities in the O, A and B horizons with increasing re‐wetting intensity. Drying and re‐wetting reduced the amount of hydrolysable plant and microbial sugars in all soil horizons. However, CO₂ and dissolved organic carbon fluxes could not explain these losses. We postulate that drying and re‐wetting triggered chemical alterations of hydrolysable sugar molecules in organic and mineral soil horizons.     

Content and composition of free and occluded particulate organic matter in a differently textured arable Cambisol as revealed by solid‐state 13C NMR spectroscopy

The composition of functional light soil organic matter pools of arable Cambisols with a gradient in clay content was investigated. Soil texture differences originate from increasing loess admixture to the parent material (coarse‐grained tertiary sediments). Using density fractionation in combination with ultrasonic dispersion, two types of particulate organic matter (POM) were obtained: (1) free POM and (2) POM occluded in soil aggregates. Both POM fractions were analyzed by elemental analysis (C, N) and CPMAS ¹³C NMR spectroscopy. With increasing clay content the amount of organic carbon stored in the occluded POM fraction increased considerably, whereas the amounts of free POM were not related to the soil clay content. With increasing soil clay contents increasing proportions of O‐alkyl C and decreasing proportions of aryl C were found for both POM fractions. The occluded POM fraction showed a higher degree of degradation as indicated by lower amounts in O‐alkyl carbon. A lower degree of POM degradation was associated with higher clay contents. Higher soil clay contents promoted the conservation of POM with a low degree of alteration. This effect of soil texture was found to be highly significant when the aryl C : O‐alkyl C ratio was used as indicator for POM decomposition rather than the alkyl C : O‐alkyl C ratio.     

Contribution of organic matter and clay minerals to the cation exchange capacity of soils

Abstract

The cation exchange capacity (CEC) at pH 7 was measured for samples of 347 A horizons and 696 B horizons of New Zealand soils. The mean CEC was 22.1 cmolc/kg for the A horizons and 15.2 cmolc/kg for the B horizons. Multiple regressions were carried out for CEC against organic carbon (C), clay content, and the content of seven groups of clay minerals. The results, significant at p <0.001, were consistent with most of the CEC arising from soil organic matter. For the samples of A horizon, the calculated CEC was 221 cmolc/kg per unit C and for the B horizons was 330 cmolc/kg C. There was also a contribution from sites on clay minerals. Multiple regression indicated that smectite had a higher CEC (70 cmolc/kg) than other minerals but it was not as high as that of type smectites; kaolin minerals had the lowest CEC. There was a significant effect of interaction between organic matter and some clay minerals on the CEC. Samples from B horizons containing allophane had lower CEC than those not containing allophane which is consistent with allophane reacting with carboxyl groups on organic matter. For the samples from the A horizons, however the CEC was higher when allophane was present.     

Characterization of hydrophobic acid fractions in water-soluble organic matter in Dystric Cambisol and in a stream in a small forested watershed: Seasonal and vertical variations in chemical properties

Abstract

Chemical properties of hydrophobic acid (HoA) fractions in water-soluble organic matter in soil and water are concerned with its interactions with mineral soil surfaces and organic pollutants. In 2004 we examined the seasonal and vertical changes in chemical properties of the HoA fraction in a Cambisol profile and compared these properties with those in the HoA fraction of an adjacent stream (aquatic humic substances) in a temperate forested watershed using high performance size exclusion chromatography (HPSEC) and ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The HoA fractions from Oi, Oe/Oa, A and B horizon soils in summer had lower O-alkyl C proportions than those recorded in samples in other seasons. The proportions of aromatic C in HoA fractions from A and B horizons were highest in summer. These seasonal variations were less significant than variations with soil depth. O-alkyl C proportions in HoA fractions decreased with increasing soil depth from the Oi to the A horizon. The HoA fractions from the B horizon showed a higher alkyl C proportion than samples from other horizons in winter and spring. These changes with soil depth from the Oi to A horizons might result from selective utilization of carbohydrate carbon by microorganisms, whereas those in the B horizon may result from sorption to mineral surfaces. The HoA fractions in the stream were similar in relative molecular weight, distribution of each type of proton and carbon species in HoA fractions from the B horizon, whereas stream HoA fractions collected in summer would be derived from organic horizons. This indicated that vertical changes in the chemical properties of HoA fractions in soil and pathways of water to the stream would largely affect the chemical properties of HoA fractions in the stream.     

Adsorption of “real” dissolved organic matter on the clay and fine silt fractions of a forested Stagnic Gleysol

Dissolved organic matter (DOM) in soils is partially adsorbed when passing through a soil profile. In most adsorption studies, water soluble organic matter extracted by water or dilute salt solutions is used instead of real DOM gained in situ by lysimeters or ceramic suction cups. We investigated the adsorption of DOM gained in situ from three compartments (forest floor leachate and soil solution from 20 cm (Bg horizon) and 60 cm depth (2Bg horizon)) on the corresponding clay and fine silt fractions (< 6.3 μm, separated together from the bulk soil) of the horizons Ah, Bg, and 2Bg of a forested Stagnic Gleysol by batch experiments. An aliquot of each clay and fine silt fraction was treated with H₂O₂ to destroy soil organic matter. Before and after the experiments, the solutions were characterized by ultra‐violet and fluorescence spectroscopy and analyzed for sulfate, chloride, nitrate, and fluoride. The highest affinity for DOM was found for the Ah samples, and the affinity decreased in the sequence Ah > Bg > 2Bg. Dissolved organic matter in the 2Bg horizon can be regarded as slightly reactive, because adsorption was low. Desorption of DOM from the subsoil samples was reflected more realistically with a non‐linear regression approach than with initial mass isotherms. The results show that the extent of DOM adsorption especially in subsoils is controlled by the composition and by the origin of the DOM used as adsorptive rather than by the mineralogical composition of the soil or by contents of soil organic matter. We recommend to use DOM gained in situ when investigating the fate of DOM in subsoils.     

Mineralogical control of organic carbon dynamics in a volcanic ash soil on La Réunion

In soil carbon dynamics, the role of physicochemical interactions between organic matter and minerals is not well understood nor quantified. This paper examines the interactions between soil organic matter and poorly crystalline aluminosilicates in a volcanic ash soil on La Réunion in the southern tropics. The soil examined is a profile composed of a surface soil (L-Ao-E-Bh) overlying four buried horizons (horizons 2Bw, 3Bw, 4Bw, 5Bw) that have all developed from successive tephra deposits. Non-destructive spectroscopy (XRD, FTIR and NMR of Si and Al) showed that the mineralogical composition varies from one buried horizon to another. Further, we show that buried horizons characterized by large amounts of crystalline minerals (feldspars, gibbsite) have the least capacity to store organic matter and the fastest carbon turnover. In contrast, buried horizons containing much poorly crystalline material (proto-imogolite and proto-imogolite allophane, denoted LP-ITM) store large amounts of organic matter which turns over very slowly. To understand the mechanism of interactions between LP-ITM and organic matter better, we focused on a horizon formed exclusively of LP-ITM. We demonstrate, using Δ¹⁴C and δ¹³C values, that even though LP-ITM is extraordinarily effective at stabilizing organic matter, C linked to LP-ITM is still in dynamic equilibrium with its environment and cycles slowly. Based on Δ¹⁴C values, we estimated the residence time of organic C as ∼ 163 000 years for the most stabilized subhorizon, a value that is comparable to that for organic carbon stabilized in Hawaiian volcanic soils. However, this calculation is likely to be biased by the presence of microcharcoal. We characterized the organo-mineral binding between organic matter and LP-ITM by ²⁷Al NMR, and found that the organic matter is not only chelated to LP-ITM, but it may also limit the polymerization of mineral phases to a stage between proto-imogolite and proto-imogolite allophane. Our results demonstrate the important role of poorly crystalline minerals in the storage of organic C, and show that mineral and organic compounds have to be studied simultaneously to understand the dynamics of organic C in the soil.     

Total lipid extracts from characteristic soil horizons in a podzol profile

The podzolization process is studied through lipids in nine characteristic podzol horizons. Organic matter accumulates particularly with aluminium in the Bh horizon, while the hard, cemented Bs horizon below this is formed mainly by iron oxides. The low soil pH seems to have no great influence on the preservation of lipids as reflected by the absolute amounts present and the presence of bacterial lipid markers throughout the profile. Independent of soil pH, lipids accumulate in organically enriched horizons. Albeit, high molecular weight organic compounds accumulate to a relatively greater extent than lipids in these horizons. A lipid signal related to the aerial parts, i.e. leaves and flowers, of Calluna is observed only in the O horizon. This ‘n‐alkane, steroid and triterpenoids’ signal is quickly lost in the underlying Ah horizon due to (bacterial) oxidation. The other total lipid extracts obtained are dominated by root‐derived compounds. In subsoil horizons rich in organic matter, i.e. the Ahb and Bh horizons, root‐derived friedooleanan and steroid compounds dominate the total lipid signal. Degraded horizons, poor in organic matter, i.e. the E2, Bhs, Bs and B/C horizons, are dominated by C₂₂ and C₂₄ω‐hydroxy acids, long‐chain (> C₂₀) n‐alkanoic acids with a strong even‐over‐odd predominance and C₂₂ and C₂₄n‐alkanols. Steroid and root‐derived triterpenoids with a friedooleanan structure have been removed from these horizons through degradation. Based on total organic carbon content and lipid composition, the formation of an E1 horizon has started, but is not yet complete. In the Ahb horizon, a contribution from buried vegetation to the total lipid signal is still present, although degradation and an input from roots have significantly altered the original signal. Overall, lipid data indicate that degradation (microbial oxidation) is an important process that should be taken into account, in addition to leaching, when describing podzolization processes in soils.     

Contribution of separate solid-phase components to the formation of the cation exchange capacity in the main genetic horizons of meadow-chestnut soils

Different types of cation exchange capacity (CEC) and related chemical properties were determined in the main genetic horizons of meadow-chestnut soils in the mesodepressions at the Dzhanybek Research Station of the Institute of Forestry of the Russian Academy of Sciences. In the A horizon, the CEC is mainly due to the organic matter from the clay and coarse fractions, which provides 36% of the soil CEC, and to labile silicates and other clay minerals of the clay fraction. In the Bt horizon, the CEC is mainly provided by the labile minerals of the clay fraction and organic matter of the clay and coarse fractions. The standard soil CEC was found to be significantly higher than the sum of the exchangeable cations in the A horizon and slightly lower than the sum of the exchangeable cations in the Bt and Bca2 horizons. This difference can be related to the fact that the NH₄⁺ ion, which is selectively adsorbed by clay minerals, is used as a displacing cation during the determination of the exchangeable bases, while the Ba²⁺ ion, which is more selectively adsorbed by organic matter, is used during the determination of the standard CEC. In all the genetic horizons, the experimentally determined value of the standard CEC almost coincides with the CEC value obtained by summing the standard CECs of the different particle-size fractions with account for their contents; hence, this parameter is additive in nature.     

Geogenic CO2 affects stabilization of soil organic matter

The soil on mofette sites is affected by ascending geogenic carbon dioxide (CO₂), which partially fills the soil atmosphere. We hypothesized that geogenic CO₂ affects the stabilization of soil organic matter (SOM) at lower partial pressures than had been discussed previously for mofette sites. We studied loamy Ah horizons (n = 22; pH 3.4–4) of the soil along a transect on a grassland mofette site in the northwest Czech Republic with CO₂ partial pressures (p(CO₂)) of up to 0.52. The samples were fractionated by particle size, density and solubility (water‐soluble organic matter (WSOM)), and analysed quantitatively for organic carbon (C) and total nitrogen (N) and qualitatively (¹³C‐NMR spectroscopy). Soil OM with a narrower C:N ratio accumulated in the clay fraction, but at p(CO₂) less than approximately 0.1 the proportion of SOM in the clay fraction relative to total SOM tended to decrease with increasing p(CO₂), whereas that of particulate organic matter (POM) fractions increased with increasing p(CO₂). We attribute the distribution of SOM among the mineral soil and POM to decreased interactions with minerals of the clay fraction. The formation of iron (Fe) hydroxides, which potentially sorb SOM, was not affected negatively by CO₂. The potential reactivity of Fe hydroxides was even positively affected by increased p(CO₂). Export of dissolved SOM into the subsoil might increase at mofette sites because of the large amounts of WSOM and decreasing interactions with minerals of the clay fraction. Therefore, our results show negative effects of CO₂ on SOM stabilization even at moderate p(CO₂).     

Sulfur K-edge XANES spectroscopy reveals differences in sulfur speciation of bulk soils, humic acid, fulvic acid, and particle size separates

X-ray absorption near edge structure (XANES) spectra at the sulfur (S) K-edge (E=2472 eV) were compared for bulk soil material, humic and fulvic acid fractions, and different particle size separates from Ah horizons of two arable Luvisols, from an O and a Bs horizon of a Podzol under Norway spruce forest, and from an H horizon of a Histosol (peat bog). In the bulk soil samples, the contribution of reduced organic S (organic mono- and disulfides) to total sulfur increased from 27% to 52%, and the contribution of ester sulfate and SO₄²⁻-S decreased from 39% to 14% of total S in the following order: arable Luvisols Ah—forested Podzol O—Histosol H. This sequence reflects the increasing organic carbon content and the decreasing O₂ availability in that order. Neither sulfonate nor inorganic sulfide was detected in any of the bulk soil samples. For all samples except the Podzol Bs, the XANES spectra of the bulk soils differed considerably from the spectra of the humic and acid fractions of the respective soils, with the latter containing less reduced S (16-44% of total S) and more oxidized S (sulfone S: 19-35%; ester sulfate S: 14-38% of total S). Also the S speciation of most particle size fractions extracted from the Ah horizon of the Viehhausen Luvisol and the Bs horizon of the Podzol was different from that of the bulk soil. For both soils, the contribution of oxidized S species to total S increased and the contribution of sulfoxides and organic mono- and disulfides decreased with decreasing particle size. Thus, sulfur K-edge XANES spectra of alkaline soil extracts, including humic and fulvic acids or of particle size separates are not representative for the S speciation of the original soil sample they are derived from. The differences can be attributed to (i) artificial changes of the sulfur speciation during alkaline extraction (conversion of reduced S into oxidized S, loss of SO₄²⁻ during purification of the extracts by dialysis) or particle size separation (carry-over of water-soluble S, such as SO₄²⁻), but also to (ii) preferential enrichment of oxidized S in hydrophilic water-soluble soil organic matter (ester sulfate) and in the clay fraction of soils (ester sulfate, adsorbed SO₄²⁻).     

Influence of fertilization and organic amendments on organic‐carbon fractions in Heilu soil on the loess plateau of China

The influence of fertilization on organic‐carbon fractions separated by density and particle size in Heilu soil (Calcic Kastanozems, FAO) was investigated in a 20‐year (1979–1999) long‐term experiment on the Loess Plateau of China. Compared to an unfertilized treatment, N application alone did not increase total organic carbon (TOC) and its fractions of density and particle size. However, the treatment of N + P fertilization significantly increased salty‐solution–soluble organic carbon (SSOC), microbial biomass C (MB‐C), and organic C associated with fine silt. When manure was applied alone and in combination with N and P fertilizer, the light fraction of organic C (LFOC), SSOC, and MB‐C were increased significantly, and the TOC was as high as that of a native Heilu soil. Organic C associated with different particle‐size fractions was also increased significantly, and the allocation of C among the fractions was altered: the proportions of C in sand (>50 μm), coarse‐silt (20–50 μm), and fine‐clay (<0.2 μm) fractions were increased whereas fine‐silt (2–20 μm) and coarse‐clay (0.2–2 μm) fractions were decreased. It is concluded that N fertilizer alone is not capable of restoring organic‐matter content in the Heilu soils of the Loess Plateau and that C‐containing material like manure and straw is necessary to produce significant increase in soil organic carbon in these soils.     

Soil organic matter and its lignin component in surface horizons of salt-affected soils of the Argentinian Pampa

Salt-affected soils differ in their chemical properties to all other soils. Sodicity and salinity may affect the soil organic matter component of these soils. In a field experiment, we investigated organic matter decomposition in nonsaline nonsodic Aquic Argiudoll, a nonsaline sodic Typic Natraquoll, nonsaline nonsodic Petrocalcic Paleudoll and a saline sodic Typic Natralboll in the Pampa Deprimida, Argentina. The objectives were to identify the degree of stabilization of organic matter by association with mineral particles in these soils and to follow in particular the fate of lignin in these soils. We measured organic carbon, total nitrogen and the extent of lignin alteration with soil depth and in various particle size fractions. The salt-affected soils contained much less organic carbon and nitrogen in their mollic epipedons than the nonsaline nonsodic soils, and bioturbation into deeper layers was restrained. In the salt-affected soils most of the organic matter was in sand-sized particles. Retarded degradation of plant residues was indicated by the pattern of lignin-derived phenols, suggesting less alteration of lignin in the salt-affected soils than in the nonsaline nonsodic soils. We suggest that this results from the effects of high pH, high sodicity, and high salinity on the microorganisms and their enzymatic activities. The high pH and high concentrations of monovalent cations decreased formation of solid organo-mineral complexes. We conclude that in the salt-affected soils oxidatively altered organic compounds are susceptible to losses in dissolved or colloidal forms, because these compounds are not stabilized against leaching and mineralization by chemical bonding to soil minerals.     

Chemical composition of young and old carbon pools throughout Cambisol and Luvisol profiles under forests

The long-term storage of soil organic matter (SOM) in forest soils is still poorly understood. In this study, particle size fractionation in combination with accelerator mass spectroscopy (AMS) and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy was applied to investigate organic carbon (OC) stabilisation in Cambisol and Luvisol profiles under spruce (Picea abies) and beech (Fagus sylvatica L.) forests. In most samples, OC was preferentially associated with <2 μm fractions. Throughout soil profiles the contribution of OC in the clay fraction to the total OC increased from 27%-53% in A horizons to 44-86% in E, B and EB horizons. The 200-2000 μm fractions from all sites and all depths showed a percentage of modern C (pmC)>100. They were enriched in ¹⁴C owing to high inputs of recent material from leaves and roots. Clearly less active material was associated with <2 and 2-20 μm fractions. This demonstrated that the particle size fractionation procedure applied to our study was capable to isolate a young OC fraction in all samples. The pmC values were strongly decreasing with depth but the decrease was much more pronounced in the fine fractions. The <2 and 2-20 μm fractions of B, E and EB horizons revealed radiocarbon ages between 512 and 4745 years before present which indicated that the SOM in those horizons was little affected by the recent vegetation. The major components of labile and stable SOM pools in topsoils and subsoils were always O/N-alkyl C (28-53%) and alkyl C (14-48%) compounds. NMR spectra of bulk soils and particle size fractions indicated that high alkyl C and O/N-alkyl C proportions throughout the soil profile are typical of Cambisols and Luvisols which were not subjected to regular burning. A relation between radiocarbon age and chemical composition throughout soil profiles was not observed. This suggests that the long-term stabilisation of SOM is mainly controlled by the existence of various mechanisms of protection offered by the soil matrix and soil minerals but not by the chemical structure of SOM itself.     

Soil properties and tree growth along an altitudinal transect in Ecuadorian tropical montane forest

In tropical montane forests, soil properties change with increasing altitude, and tree‐growth decreases. In a tropical montane forest in Ecuador, we determined soil and tree properties along an altitudinal transect between 1960 and 2450 m asl. In different vegetation units, all horizons of three replicate profiles at each of eight sites were sampled and height, basal area, and diameter growth of trees were recorded. We determined pH and total concentrations of Al, C, Ca, K, Mg, Mn, N, Na, P, S, Zn, polyphenols, and lignin in all soil horizons and in the mineral soil additionally the effective cation‐exchange capacity (CEC). The soils were Cambisols, Planosols, and Histosols. The concentrations of Mg, Mn, N, P, and S in the O horizons and of Al, C, and all nutrients except Ca in the A horizons correlated significantly negatively with altitude. The C : N, C : P, and C : S ratios increased, and the lignin concentrations decreased in O and A horizons with increasing altitude. Forest stature, tree basal area, and tree growth decreased with altitude. An ANOVA analysis indicated that macronutrients (e.g., N, P, Ca) and micronutrients (e.g., Mn) in the O layer and in the soil mineral A horizon were correlated with tree growth. Furthermore, lignin concentrations in the O layer and the C : N ratio in soil affected tree growth. These effects were consistent, even if the effect of altitude was accounted for in a hierarchical statistical model. This suggests a contribution of nutrient deficiencies to reduced tree growth possibly caused by reduced organic‐matter turnover at higher altitudes.     

Changes in soil organic matter composition are associated with forest encroachment into grassland with long-term fire history

This study investigates if Araucaria forest (C₃ metabolism) expansion on frequently burnt grassland (C₄ metabolism) in the southern Brazilian highland is linked to the chemical composition of soil organic matter (SOM) in non‐allophanic Andosols. We used the ¹³C/¹²C isotopic signature to group heavy organo‐mineral fractions according to source vegetation and ¹³C NMR spectroscopy, lignin analyses (CuO oxidation) and measurement of soil colour lightness to characterize their chemical compositions. Large proportions of aromatic carbon (C) combined with small contents of lignin‐derived phenols in the heavy fractions of grassland soils and grass‐derived lower horizons of Araucaria forest soils indicate the presence of charred grass residues in SOM. The contribution of this material may have led to the unusual increase in C/N ratios with depth in burnt grassland soils and to the differentiation of C₃‐ and C₄‐derived SOM, because heavy fractions from unburnt Araucaria forest and shrubland soils have smaller proportions of aromatic C, smaller C/N ratios and are paler compared with those with C₄ signatures. We found that lignins are not applicable as biomarkers for plant origin in these soils with small contents of strongly degraded and modified lignins as the plant‐specific lignin patterns are absent in heavy fractions. In contrast, the characteristic contents of alkyl C and O/N‐alkyl C of C₃ trees or shrubs and C₄ grasses are reflected in the heavy fractions. They show consistent changes of the (alkyl C)/(O/N‐alkyl C) ratio and the ¹³C/¹²C isotopic signature with soil depth, indicating their association with C₄ and C₃ vegetation origin. This study demonstrates that soils may preserve organic matter components from earlier vegetation and land‐use, indicating that the knowledge of past vegetation covers is necessary to interpret SOM composition.