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.     

Organo-mineral associations in sandy acid forest soils: importance of specific surface area, iron oxides and micropores

Organo-mineral associations stabilize soil organic matter, though the mechanisms by which they do so are unclear. We used particle-size fractions < 6.3 μm of two soils to examine the importance of Fe oxides, short-range order Al silicates and the surface areas of minerals and micropores on the formation of organo-mineral associations. In the subsoil Fe oxides were most strongly statistically correlated with the mineral-bound organic carbon. We therefore assume that they are the most important substrates for the formation of organo-mineral associations. There is no indication that this is caused by physical protection of organic matter in their micropores (< 2 nm). In the Haplic Podzol, dithionite–citrate–bicarbonate-soluble short-range order Al silicates may also play a role. Fe oxide particles were calculated to offer specific surface areas of ∼ 200 m² g⁻¹ (goethite) and ∼ 800 m² g⁻¹ (ferrihydrite), corresponding to crystal diameters of only a few nm. We assume that the resulting large amount of oxide-specific reactive surface sites (conditionally charged hydroxyl groups) is responsible for their dominant role as sorbents. With maximum C loadings of 1.3 mg C per m² Fe oxide for the Dystric Cambisol and 1.1 mg C per m² Fe oxide + short-range order Al silicates for the Haplic Podzol the subsoils of both soils seem to have reached saturation with respect to organic matter sorption. In contrast to subsoil horizons, organo-mineral associations from topsoils contain much larger amounts of organic matter. Here a larger C loading on Fe oxides or a greater importance of other sorbents in addition to the oxides must be assumed.     

Contribution of dissolved organic matter to carbon storage in forest mineral soils

Dissolved organic matter (DOM) is often considered the most labile portion of organic matter in soil and to be negligible with respect to the accumulation of soil C. In this short review, we present recent evidence that this view is invalid. The stability of DOM from forest floor horizons, peats, and topsoils against microbial degradation increases with advanced decomposition of the parent organic matter (OM). Aromatic compounds, deriving from lignin, likely are the most stable components of DOM while plant‐derived carbohydrates seem easily degradable. Carbohydrates and N‐rich compounds of microbial origin produced during the degradation of DOM can be relatively stable. Such components contribute much to DOM in the mineral subsoil. Sorption of DOM to soil minerals and (co‐)precipitation with Al (and probably also with Fe), especially of the inherently stable aromatic moieties, result in distinct stabilization. In laboratory incubation experiments, the mean residence time of DOM from the Oa horizon of a Haplic Podzol increased from <30 y in solution to >90 y after sorption to a subsoil. We combined DOM fluxes and mineralization rate constants for DOM sorbed to minerals and a subsoil horizon, and (co‐)precipitated with Al to estimate the potential contribution of DOM to total C in the mineral soil of a Haplic Podzol in Germany. The contribution of roots to DOM was not considered because of lack of data. The DOM‐derived soil C ranges from 20 to 55 Mg ha^–1 in the mineral soil, which represents 19%–50% of the total soil C. The variation of the estimate reflects the variation in mineralization rate constants obtained for sorbed and (co‐)precipitated DOM. Nevertheless, the estimates indicate that DOM contributes significantly to the accumulation of stable OM in soil. A more precise estimation of DOM‐derived C in soils requires mineralization rate constants for DOM sorbed to all relevant minerals or (co‐)precipitated with Fe. Additionally, we need information on the contribution of sorption to distinct minerals as well as of (co‐)precipitation with Al and Fe to DOM retention.     

Microbial community composition shapes enzyme patterns in topsoil and subsoil horizons along a latitudinal transect in Western Siberia

Soil horizons below 30 cm depth contain about 60% of the organic carbon stored in soils. Although insight into the physical and chemical stabilization of soil organic matter (SOM) and into microbial community composition in these horizons is being gained, information on microbial functions of subsoil microbial communities and on associated microbially-mediated processes remains sparse. To identify possible controls on enzyme patterns, we correlated enzyme patterns with biotic and abiotic soil parameters, as well as with microbial community composition, estimated using phospholipid fatty acid profiles. Enzyme patterns (i.e. distance-matrixes calculated from these enzyme activities) were calculated from the activities of six extracellular enzymes (cellobiohydrolase, leucine-amino-peptidase, N-acetylglucosaminidase, chitotriosidase, phosphatase and phenoloxidase), which had been measured in soil samples from organic topsoil horizons, mineral topsoil horizons, and mineral subsoil horizons from seven ecosystems along a 1500 km latitudinal transect in Western Siberia. We found that hydrolytic enzyme activities decreased rapidly with depth, whereas oxidative enzyme activities in mineral horizons were as high as, or higher than in organic topsoil horizons. Enzyme patterns varied more strongly between ecosystems in mineral subsoil horizons than in organic topsoils. The enzyme patterns in topsoil horizons were correlated with SOM content (i.e., C and N content) and microbial community composition. In contrast, the enzyme patterns in mineral subsoil horizons were related to water content, soil pH and microbial community composition. The lack of correlation between enzyme patterns and SOM quantity in the mineral subsoils suggests that SOM chemistry, spatial separation or physical stabilization of SOM rather than SOM content might determine substrate availability for enzymatic breakdown. The correlation of microbial community composition and enzyme patterns in all horizons, suggests that microbial community composition shapes enzyme patterns and might act as a modifier for the usual dependency of decomposition rates on SOM content or C/N ratios.     

Alkyl C and hydrophobicity in B and C horizons of an acid forest soil

Aliphatic C most probably derived from ester‐bound moieties was found to be present in sandy subsoil horizons. The hydrophobic nature of such compounds may increase their stabilization potential. Therefore, the aim of this study was to investigate the potential of aliphatic compounds in mineral soil horizons along a Dystric Cambisol profile under beech forest to increase hydrophobicity. The conceptual approach included the analyses of soil samples before and after solvent extraction and base hydrolysis for elemental and isotopic composition. Additionally, the advancing contact angle was measured to quantify hydrophobicity. Curie‐point pyrolysis GC/MS was carried out to characterize the nature of alkyl C present in subsoil samples. A close correlation between the ¹⁴C activity and the stable‐C‐isotope ratio (δ¹³C) indicates isotopic fractionation upon C stabilization in subsoils. Free lipids contributed less than 10% to the organic C found in subsoil horizons. Base hydrolysis revealed very high amounts of hydroxyalkanoic acids in the B horizons of the acid forest soil. Hydrophobicity of SOM was not found to be correlated to esterified‐ or free‐lipid content. The contact angle was in a similar range for all bulk soil horizons, suggesting greater hydrophobicity of organic matter in subsoil horizons considering their very low concentrations of organic C compared to the A horizon. The quantity and nature of pyrolysis products change with increasing depth in the soil profile. Aliphatic products cannot be detected in B and C horizons by Curie‐point pyrolysis GC/MS.     

Organic matter stabilization in two Andisols of contrasting age under temperate rain forest

Recent studies with Andisols show that the carbon (C) stabilization capacity evolves with soil age relative to the evolution of the mineral phase. However, it is not clear how soil mineralogical changes during pedogenesis are related to the composition of soil organic matter (SOM) and ¹⁴C activity as an indicator for the mean residence time of soil organic matter (SOM). In the present study, we analyzed the contribution of allophane and metal–SOM complexes to soil C stabilization. Soil organic matter was analyzed with solid-state ¹³C nuclear magnetic resonance spectroscopy. Additionally, the soil was extracted with Na-pyrophosphate (Al_p, Fe_p) and oxalate (Al_o, Si_o, and Fe_o). Results supported the hypothesis that allophane plays a key role for SOM stabilization in deep and oldest soil, while SOM stabilization by metal (Al and Fe) complexation is more important in the surface horizons and in younger soils. The metal/C_p ratio (C_p extracted in Na-pyrophosphate), soil pH, and radiocarbon age seemed to be important indicators for formation of SOM–metal complexes or allophane in top- and subsoils of Andisols. Changes in main mineral stabilization agents with soil age do not influence SOM composition. We suggest that the combination of several chemical parameters (Al_p, Fe_p and C_p, metal/C_p ratio, and pH) which change through soil age controls SOM stabilization.     

Amount and composition of clay-associated soil organic matter in a range of kaolinitic and smectitic soils

In the global carbon cycle, soil organic matter (SOM) is a major source/sink of atmospheric carbon. Clay minerals stabilize part of the SOM through mineral–organic matter binding. Stabilization of organic matter is essential for tropical soils. Since the climatic conditions of the tropics favor decomposition of organic matter, tropical soils would be very poor in organic matter without this stabilization process. This research aims at determining the effect of clay mineralogy on the amount and composition of organic matter that is bound to the mineral surface. We focused on organic matter that is associated with kaolinite and smectite. We characterized kaolinite- and smectite-associated SOM in soils from seven countries, employing ¹³C NMR spectroscopy and Py-GC/MS. The content of carbon in the total clay-size fraction showed no significant difference between kaolinitic and smectitic soils. This suggests that the total amount of organic carbon in the clay-size fraction is independent of the clay mineralogy. We first extracted the clay fraction with NaOH and thereafter with Na₄P₂O₇. About half of the kaolinite-associated SOM was extractable by NaOH. In the smectitic soils, pyrophosphate extracted more organic carbon than did NaOH. The Py-GC/MS and NMR results indicate that kaolinite-associated SOM is enriched in polysaccharide products, while smectite-associated organic matter contains many aromatic compounds. We suggest that different clay minerals use different binding mechanisms to complex SOM. As a result, the composition of clay-associated organic matter would be influenced by the type of clay that is dominantly present in the soil.     

从高山火山灰中提取铝, 铁和有机碳的可供选择的方法

Montane volcanic ash soils contain disproportionate amounts of soil organic carbon and thereby play an often underestimated role in the global carbon cycle.Given the central role of Al and Fe in stabilizing organic matter in volcanic ash soils,we assessed various extraction methods of Al,Fe,and C fractions from montane volcanic ash soils in northern Ecuador,aiming at elucidating the role of Al and Fe in stabilizing soil organic matter(SOM).We found extractions with cold sodium hydroxide,ammonium oxalate/oxalic acid,sodium pyrophosphate,and sodium tetraborate to be particularly useful.Combination of these methods yielded information about the role of the mineral phase in stabilizing organic matter and the differences in type and degree of complexation of organic matter with Al and Fe in the various horizons and soil profiles.Sodium tetraborate extraction proved the only soft extraction method that yielded simultaneous information about the Al,Fe,and C fractions extracted.It also appeared to differentiate between SOM fractions of different stability.The fractions of copper chloride-and potassium chloride-extractable Al were useful in assessing the total reactive and toxic Al fractions,respectively.The classical subdivision of organic matter into humic acids,fulvic acids,and humin added little useful information.The use of fulvic acids as a proxy for mobile organic matter as done in several model-based approaches seems invalid in the soils studied.     

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.     

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).     

Clay minerals,oxyhydroxide formation,element leaching and humus development in volcanic soils

A weathering sequence with soils developing on volcanic, trachy-basaltic parent materials with ages ranging from 100–115,000 years in the Etna region served as the basis to analyse and calculate the accumulation and stabilisation mechanisms of soil organic matter (SOM), the transformation of pedogenic Fe and Al, the formation and transformation of clay minerals, the weathering indices and, by means of mass-balance calculations, net losses of the main elements. Although the soils were influenced by ash depositions during their development and the soil on the oldest lava flow developed to a great extent under a different climate, leaching of elements and mineral formation and transformation could still be measured. Leaching of major base cations coupled with a corresponding passive enrichment of Al or Fe was a main weathering mechanism and was especially pronounced in the early stages of soil formation due to mineral or glass weathering. With time, the weathering indexes (such as the (K + Ca)/Ti ratio) tend to an asymptotic value: chemical and mineralogical changes between 15,000 and 115,000 years in the A and B horizons were small. In contrast to this, the accumulation of newly formed ITM (imogolite type materials) and ferrihydrite showed a rather linear behaviour with time. Weathering consisted of the dissolution of primary minerals such as plagioclase, pyroxenes or olivine, the breakdown of volcanic glass and the formation of secondary minerals such as ITM and ferrihydrite. The main mineral transformations were volcanic glass ? imogolite ? kaolinite (clay fraction). In the most weathered horizons a very small amount of 2:1 clay minerals could be found that were probably liberated from the inner part of volcanic glass debris. The rate of formation and transformation of 2:1 clay minerals in the investigated soils was very low; no major changes could be observed even after 115,000 years of soil evolution. This can be explained by the addition of ash and the too low precipitation rates. In general, soil erosion played a subordinate role, except possibly for the oldest soils (115,000 years). The youngest soils with an age < 2000 years had the highest accumulation rate of organic C (about 3.0 g C/m²/year). After about 15,000 years, the accumulation rate of organic C in the soils tended to zero. Soil organic carbon reached an asymptotic value with abundances close to 20 kg/m² after about 20,000 years. In general, the preservation and stabilisation of SOM were due to poorly crystalline Al- and Fe-phases (pyrophosphate-extractable), kaolinite and the clay content. These parameters correlated well with the organic C. Imogolite-type material did not contribute significantly to the stabilisation of soil organic matter.     

Chemical structure of humic acids in biosolids-amended soils as revealed by NMR spectroscopy

We used NMR spectroscopy to characterize humid acids extracted from soils that had received long-term application of 2 levels of biosolids to evaluate the soil organic matter (SOM) stability in biosolids-amended soils. The study also quantified fulvic acids (FAs), humic acids (HAs) and Fe/Al oxides. The soils were collected in 2004 from 7 fields, in Fulton County, southwestern Illinois, which received biosolids at a cumulative rate of 0 (control), 554 (low biosolids) and 1,066 (high biosolids) Mg ha⁻¹. The application of biosolids increased both FA and HA contents, but biosolids-amended soil and control soil did not differ in FA/HA ratio. Biosolids application had no effect on water-soluble organic carbon content. Biosolids application increased the presence of Fe/Al in the SOM complex and lowered its C/Fe and C/Al ratios. ¹³C NMR spectra showed increased alkyl C and decreased aromatic C content in soil HAs with the application of biosolids, and the extent of such changes was higher with high than low biosolids treatment. Under biosolids application, the soil HAs’ C structure shifts from O-alkyl-dominant to alkyl-dominant. Biosolids application does not decrease SOM stability but rather increases the stability of soil humic substances.     

Properties and bioavailability of particulate and mineral‐associated organic matter in Arctic permafrost soils,Lower Kolyma Region,Russia

Permafrost degradation may cause strong feedbacks of arctic ecosystems to global warming, but this will depend on if, and to what extent, organic matter (OM) is protected against biodegradation by mechanisms other than freezing and anoxia. Here, we report on the amount, chemical composition and bioavailability of particulate (POM) and mineral‐associated OM (MOM) in permafrost soils of the East Siberian Arctic. The average total organic carbon (OC) stock across all soils was 24.0 ± 6.7 kg m^?2 within 100 cm soil depth. Density fractionation (density cut‐off 1.6 g cm^?3) revealed that 54 ± 16% of the total soil OC and 64 ± 18% of OC in subsoil horizons was bound to minerals. As well as sorption of OM to clay‐sized minerals (R² = 0.80; P < 0.01), co‐precipitation of OM with hydrolyzable metals may also transfer carbon into the mineral‐bound fraction. Carbon:nitrogen ratios, stable carbon and nitrogen isotopes, ¹³C‐NMR and X‐ray photoelectron spectroscopy showed that OM is transformed in permafrost soils, which is a prerequisite for the formation of mineral‐organic associations. Mineral‐associated OM in deeper soil was enriched in ¹³C and ¹⁵N, and had narrow C:N and large alkyl C:(O‐/N‐alkyl C) ratios, indicating an advanced stage of decomposition. Despite being up to several thousands of years old, when incubated under favourable conditions (60% water‐holding capacity, 15°C, adequate nutrients, 90 days), only 1.5–5% of the mineral‐associated OC was released as CO₂. In the topsoils, POM had the largest mineralization but was even less bioavailable than the MOM in subsoil horizons. Our results suggest that the formation of mineral‐organic associations acts as an important additional factor in the stabilization of OM in permafrost soils. Although the majority of MOM was not prone to decomposition under favourable conditions, mineral‐organic associations host a readily accessible carbon fraction, which may actively participate in ecosystem carbon exchange.     

Stabilised carbon in subsoil horizons is located in spatially distinct parts of the soil profile

Soil organic matter (SOM) stabilisation in subsoil horizons received much attention in recent years, due to the presence of compounds with very long residence times. The reasons for enhanced organic carbon stabilisation in subsoil horizons are poorly understood. In this study, we characterised SOM in adjacent soil compartments with different pedological functioning. We sampled SOM in visually identifiable zones in form of tongues and the adjacent soil matrix from deep soil horizons (60-140 cm depth) of 3 profiles under agricultural land. The samples were analysed for elemental and isotopic composition, radiocarbon age, chemical composition and lignin signature. The objective of the study was to examine if the tongues are characterised by contrasting carbon amounts and composition with regards to the soil matrix.Our results indicate that tongues have two times higher carbon content and are depleted in ¹⁵N with regards to the adjacent soil matrix. SOM in the tongues is characterised by up to modern radiocarbon ages, whereas SOM in the adjacent soil matrix is several thousand years old. Twenty percent more HF soluble carbon in the soil matrix suggest that more mineral bound, highly mobile SOM is present compared to tongues. Differences in chemical composition concern the lignin component, which seems to be preserved in the soil matrix. These data may be explained by different functioning in the two parts of the soil profile. In tongues, fresh carbon input by preferential flow and/or roots may lead to higher SOM turnover compared to the soil matrix. This heterogeneous distribution of stabilised SOM must be taken into account, when studying carbon sequestration in deep soil horizons.     

Black carbon contribution to soil organic matter composition in tropical sloping land under slash and burn agriculture

Tropical soils are generally depleted in organic carbon (OC) due to environmental conditions favouring decomposition and mineralisation of soil organic matter (SOM). In Northern Laos, sloping soils are subjected to slash and burn agriculture, which leads to production of black carbon (BC), a stable SOM fraction. BC may directly influence the quantity and quality of SOM sequestered in tropical soils. The aim of this study was to quantify BC content and evaluate its impact on the chemical and stable isotope composition of SOM along a catena composed of Dystrochrepts at the bottom of the slope, Alfisols (midslope) and Inceptisols at the top of the slope for different burning frequencies. Six soil profiles, situated on a slope ranging from a river bank to the summit of a hill, were sampled. The stable isotope compositions (¹³C and ¹⁵N) of samples from both organo-mineral A and mineral B and C horizons were determined. The chemical composition of SOM analysed by ¹³C CPMAS NMR spectroscopy and the contribution of BC determined by dichromate oxidation were compared to OC and iron oxide content as well as land management including the burning cycle.The highest C contents were recorded at midslope positions. At any position on the slope, δ¹³C and δ¹⁵N ratios showed an enrichment in ¹³C and ¹⁵N with increasing soil depth. The OC content of soil horizons was related to their aryl C content, which is the component most likely driven by BC inputs. The BC contributions analysed by dichromate oxidation ranged from 3% to 7% of total OC. A positive correlation was obtained between aryl C and the BC content of SOM. Comparison of BC content and stable isotope composition of SOM showed that BC influenced the δ¹³C and the δ¹⁵N stable isotope ratios of these soils. BC was not associated with the mineral phase. The highest BC contents were measured under intensive slash and burn practice in the vicinity of the boundary of Alfisols at the top of the slope, where erosion was severe. Therefore, BC, a SOM component strongly influencing OC sequestration of these soils, is susceptible to translocation down the slope.     

Towards understanding of carbon stocks and stabilization in volcanic ash soils in natural Andean ecosystems of northern Ecuador

Volcanic ash soils contain very large stocks of soil organic matter (SOM) per unit area. Consequently, they constitute potential sources or sinks for the greenhouse gas carbon dioxide. Whether soils become a net carbon source or sink with climate and/or land‐use change depends on the stability of SOM against decomposition, which is influenced by stabilization mechanisms in the soil. To quantify organic carbon stocks and to clarify the importance of chemical and physical soil characteristics for carbon stabilization in volcanic ash soils, we applied selective extraction techniques, performed X‐ray diffraction analysis of the clay fraction and estimated pore‐size distribution of soils under natural upper montane forest and grassland (páramo) in the Ecuadorian Andes. Our results show that organic carbon stocks under both vegetation types are roughly twice as large as previously reported global averages for volcanic ash soils. SOM stabilization is suggested to be dominantly influenced by the following chemical and physical soil characteristics: (i) direct stabilization of SOM in organo‐metallic (Al‐humus) complexes, explaining at most 40% of carbon accumulation, (ii) indirect protection of SOM (notably aliphatic compounds) through low soil pH and toxic levels of Al, and probably also (iii) physical protection of SOM caused by a very large micro‐porosity. Moreover, in the case of the forest soils, inherent recalcitrance of OM itself was responsible for substantial accumulation in ectorganic horizons. Both vegetation types contributed to soil acidification, thus increasing SOM accumulation.     

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.     

Sodium hypochlorite oxidation reduces soil organic matter concentrations without affecting inorganic soil constituents

Oxidative treatment can isolate a stable organic matter pool in soils for process studies of organic matter stabilization. Wet oxidation methods using hydrogen peroxide are widely used for that purpose, but are said to modify poorly crystalline soil constituents. We investigated the effect of a modified NaOCl oxidation (pH 8) on the mineral composition of 12 subsoils (4.9–38.2 g organic C kg^?1) containing varying amounts of poorly crystalline mineral phases, i.e. 1.1–20.5 g oxalate‐extractable Fe kg^?1, and of different phyllosilicate mineralogy. Post‐oxidative changes in mineral composition were estimated by (i) the determination of elements released into the NaOCl solution, (ii) the difference in dithionite‐ and oxalate‐extractable Si, Al and Fe, and (iii) the specific surface areas (SSAs) of the soils. The NaOCl procedure reduced the organic C concentrations by 12–72%. The amounts of elements released into the NaOCl extracts were small (≤ 0.14 g kg^?1 for Si, ≤ 0.13 g kg^?1 for Al, and ≤ 0.03 g kg^?1 for Fe). The SSA data and the amounts of dithionite‐ and oxalate‐extractable elements suggest that the NaOCl oxidation at pH 8 does not attack pedogenic oxides and hydroxides and only slightly dissolves Al from the poorly crystalline minerals. Therefore, we recommend NaOCl oxidation at pH 8 for the purpose of isolating a stable organic matter pool in soils for process studies of organic matter stabilization.     

Mechanisms controlling the mobility of dissolved organic matter, aluminium and iron in podzol B horizons

The processes governing the (im)mobilization of Al, Fe and dissolved organic matter (DOM) in podzols are still subject to debate. In this study we investigated the mechanisms of (im)mobilization of Al, Fe and organic matter in the upper and lower B horizons of two podzols from the Netherlands that are in different stages of development. We equilibrated batches of soil material from each horizon with DOM solutions obtained from the Oh horizon of the corresponding soil profiles. We determined the amount of (im)mobilized Al, Fe and DOM after addition of Al and Fe at pH 4.0 and 4.5 and initial dissolved organic carbon (DOC) concentrations of 10 mg C litre^?1 or 30 mg C litre^?1, respectively. At the combination of pH and DOC concentrations most realistic for the field situation, organic matter was retained in all horizons, the most being retained in the lower B horizon of the well‐developed soil and the least in the upper B horizon of the younger profile. Organic matter solubility seemed to be controlled mainly by precipitation as organo‐metal complexes and/or by adsorption on freshly precipitated solid Al‐ and Fe‐phases. In the lower B horizons, at pH 4.5, solubility of Al and Fe appeared to be controlled mainly by the equilibrium with secondary solid Al‐ and Fe‐phases. In the upper B horizons, the solubility of Al was controlled by adsorption processes, while Fe still precipitated as inorganic complexes as well as organic complexes in spite of the prevailing more acidic pH. Combined with a previous study of eluvial horizons from the same profiles, the results confirm the important role of organic matter in the transport of Al and Fe to create illuvial B horizons initially and subsequently deepening and differentiating them into Bh and Bs horizons.     

Organic matter of subsoil horizons under broadleaved forest: Highly processed or labile and plant-derived?

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