Pathways of litter C by formation of aggregates and SOM density fractions: Implications from 13C natural abundance

Aggregate formation is a key process of soil development, which promotes carbon (C) stabilization by hindering decomposition of particulate organic matter (POM) and its interactions with mineral particles. C stabilization processes lead to ¹³C fractionation and consequently to various δ¹³C values of soil organic matter (SOM) fractions. Differences in δ¹³C within the aggregates and fractions may have two reasons: 1) preferential stabilization of organic compounds with light or heavy δ¹³C and/or 2) stabilization of organic materials after passing one or more microbial utilization cycles, leading to heavier δ¹³C in remaining C. We hypothesized that: 1) ¹³C enrichment between the SOM fractions corresponds to successive steps of SOM formation; 2) ¹³C fractionation (but not the δ¹³C signature) depends mainly on the transformation steps and not on the C precursors. Consequently, minimal differences between Δ¹³C of SOM fractions between various ecosystems correspond to maximal probability of the SOM formation pathways.We tested these hypotheses on three soils formed from cover loam during 45 years of growth of coniferous or deciduous forests or arable crops. Organic C pools in large macroaggregates, small macroaggregates, and microaggregates were fractionated sequentially for four density fractions to obtain free POM with ρ < 1.6 g cm⁻³, occluded POM with two densities (ρ < 1.6 and 1.6–2.0 g cm⁻³), and mineral fraction (ρ > 2.0 g cm⁻³).The density fractions were ¹³C enriched in the order: free POM < light occluded POM < heavy occluded POM < mineral fraction. This, as well as their C/N ratios confirmed that free POM was close to initial plant material, whereas the mineral fraction was the most microbially processed. To evaluate the successive steps of SOM formation, the Δ¹³C values between δ¹³C of SOM fractions and δ¹³C of bulk SOM were calculated. The Δ¹³C indicated that, parallel with biochemical transformations, the physical disintegration strongly contributed to the formation of free and occluded light POM. In contrast, biochemical transformations were more important than physical disintegration for formation of heavy occluded POM from light occluded POM. This was confirmed by review of 70 Δ¹³C values from other studies analyzed Δ¹³C depending on the density of SOM fractions. Accordingly, the successive steps of SOM formation were: fLF_<1.6 = oLF_<1.6 → oDF_1.6–2.0 = MF_>2.0. The obtained steps of C stabilization were independent on the initial precursors (litter of coniferous forest, deciduous forest or grasses).To test the second hypothesis, we proposed an extended scheme of C flows between the 3 aggregate size classes and 4 SOM fractions. Δ¹³C enrichment of the SOM fractions showed that the main direction of C flows within the aggregates and SOM fractions was from the macroaggregate-free POM to the mineral microaggregate fraction. This confirmed the earlier concept of SOM turnover in aggregates, but for the first time quantified the C flows within the aggregates and SOM density fractions based on δ¹³C values. So, the new ¹³C natural abundance approach is suitable for analysis of C pathways by SOM formation under steady state without ¹³C or ¹⁴C labeling.     

Organic matter in density fractions of water-stable aggregates in silty soils: Effect of land use

The location of soil organic matter (SOM) within the soil matrix is considered a major factor determining its turnover, but quantitative information about the effects of land cover and land use on the distribution of SOM at the soil aggregate level is rare. We analyzed the effect of land cover/land use (spruce forest, grassland, wheat and maize) on the distribution of free particulate organic matter (POM) with a density <1.6 g cm⁻³ (free POM_<1.6), occluded particulate organic matter with densities <1.6 g cm⁻³ (occluded POM_<1.6) and 1.6-2.0 g cm⁻³ (occluded POM_1.6-2.0) and mineral-associated SOM (>2.0 g cm⁻³) in size classes of slaking-resistant aggregates (53-250, 250-1000, 1000-2000, >2000 μm) and in the sieve fraction <53 μm from silty soils by applying a combined aggregate size and density fractionation procedure. We also determined the turnover time of soil organic carbon (SOC) fractions at the aggregate level in the soil of the maize site using the ¹³C/¹²C isotope ratio. SOM contents were higher in the grassland soil aggregates than in those of the arable soils mainly because of greater contents of mineral-associated SOM. The contribution of occluded POM to total SOC in the A horizon aggregates was greater in the spruce soil (23-44%) than in the grassland (11%) and arable soils (19%). The mass and carbon content of both the free and occluded POM fractions were greater in the forest soil than in the grassland and arable soils. In all soils, the C/N ratios of soil fractions within each aggregate size class decreased in the following order: free POM_<1.6>occluded POM_<1.6-2.0>mineral-associated SOM. The mean age of SOC associated with the <53 μm mineral fraction of water-stable aggregates in the Ap horizon of the maize site varied between 63 and 69 yr in aggregates >250 μm, 76 yr in the 53-250 μm aggregate class, and 102 yr in the sieve fraction <53 μm. The mean age of SOC in the occluded POM increased with decreasing aggregate size from 20 to 30 yr in aggregates >1000 μm to 66 yr in aggregates <53 μm. Free POM had the most rapid rates of C-turnover, with residence times ranging from 10 yr in the fraction >2000 μm to 42 yr in the fraction 53-250 μm. Results indicated that SOM in slaking-resistant aggregates was not a homogeneous pool, but consisted of size/density fractions exhibiting different composition and stability. The properties of these fractions were influenced by the aggregate size. Land cover/land use were important factors controlling the amount and composition of SOM fractions at the aggregate level.     

Dynamics of 13C‐labeled mustard litter (Sinapis alba) in particle‐size and aggregate fractions in an agricultural cropland with high‐ and low‐yield areas

The application of ¹³C‐labeled litter enables to study decomposition processes as well as the allocation of litter‐derived carbon to different soil C pools. ¹³Carbon‐labeled mustard litter was used in order to compare decomposition processes in an agricultural cropland with high‐yield (HY) and low‐yield (LY) areas, the latter being characterized by a finer texture and a lower organic‐C (OC) content. After tracer application, ¹³C concentrations were monitored in topsoil samples in particulate organic matter (POM) and in fine mineral fractions (silt‐ and clay‐sized fractions). After 568 d, approximately 5% and 10% of the initial ¹³C amount were found in POM fractions of LY and HY areas, respectively. Higher amounts were found in POM occluded in aggregates than in free POM. Medium‐term (0.5–2 y) storage of the initial ¹³C in fine silt‐ and clay‐sized fractions amounts to 10% in HY and LY soils, with faster enrichment but also faster disappearance of the ¹³C signal from LY soils. Amounts of 80%–90% of the added ¹³C were mineralized or leached in the observed period. Decomposition of free POM was faster in HY than in LY areas during the first year, but the remaining ¹³C amounts in occluded‐POM fractions were higher in HY soils after 568 d. High‐yield and low‐yield areas showed different ¹³C dynamics in fine mineral fractions. In LY soils, ¹³C amounts and concentrations in mineral‐associated fractions increased within 160 d after application and decreased in the following time period. In HY areas, a significant increase in ¹³C amounts did not occur until after 568 d. The results indicate initially faster decomposition processes in HY than in LY areas due to different soil conditions, such as soil texture and water regime. The higher silt and clay contents of LY areas seem to promote a faster aggregate formation and turnover, leading to a closer contact between POM and mineral surfaces in this area. This favors the OC storage in fine mineral fractions in the medium term. Lower aggregate formation and turnover in the coarser textured HY soil leads to a delayed C stabilization in silt‐ and clay‐sized fractions.     

Soil organic carbon in density fractions of tropical soils under forest – pasture – secondary forest land use changes

Our knowledge of effects of land use changes and soil types on the storage and stability of different soil organic carbon (SOC) fractions in the tropics is limited. We analysed the effect of land use (natural forest, pasture, secondary forest) on SOC storage (depth 0–0.1 m) in density fractions of soils developed on marine Tertiary sediments and on volcanic ashes in the humid tropics of northwest Ecuador. The origin of organic carbon stored in free light (< 1.6 g cm^?3) fractions, and in two light fractions (LF) occluded within aggregates of different stability, was determined by means of δ¹³C natural abundance. Light occluded organic matter was isolated in a first step after aggregate disruption by shaking aggregates with glass pearls (occluded I LF) and in a subsequent step by manual destruction of the most stable microaggregates that survived the first step (occluded II LF). SOC storage in LFs was greater in volcanic ash soils (7.6 ± 0.6 Mg C ha^?1) than in sedimentary soils (4.3 ± 0.3 Mg C ha^?1). The contribution of the LFs to SOC storage was greater in natural forest (19.2 ± 1.2%) and secondary forest (16.6 ± 1.0%) than in pasture soils (12.8 ± 1.0%), independent of soil parent material. The amount of SOC stored in the occluded I LF material increased with increasing silt + clay content (sedimentary soils, r = 0.73; volcanic ash soils, r = 0.58) and aggregation (sedimentary soils, r = 0.52; volcanic ash soils, r = 0.45). SOC associated with occluded I LF, had the smallest proportion of new, pasture‐derived carbon, indicating the stabilizing effect of aggregation. Fast turnover of the occluded II LF material, which was separated from highly stable microaggregates, strongly suggested that this fraction is important in the initial process of aggregate formation. No pasture‐derived carbon could be detected in any density fractions of volcanic ash soils under secondary forest, indicating fast turnover of these fractions in tropical volcanic ash soils.     

Land‐use change in subalpine grassland soils: Effect on particulate organic carbon fractions and aggregation

Abandonment of mountain grassland often changes vegetation composition and litter quantity and quality, but related effects on labile soil organic matter (SOM) are largely unknown. The aim of this study was to investigate the impacts of grassland management and abandonment on soil carbon distribution in light (< 1.6 g cm^–3) particulate organic matter (POM) and aggregation along a gradient of management intensity including hay meadows, pastures, and abandoned grasslands. The reduction of management intensity is an interregional phenomenon throughout the European Alps. We therefore selected sites from two typical climate regions, namely at Stubai Valley, Austria (MAT: 3°C, MAP: 1097 mm) and Matsch Valley, Italy (MAT: 6.6°C, MAP: 527 mm), to evaluate effects of land‐use change in relation to climate. Free water‐floatable and free POM (wPOM, fPOM), and an occluded POM fraction (oPOM), were isolated from three water‐stable aggregate size classes (2–6.3 mm, 0.25–2 mm, < 0.25 mm) using density fractionation. Aggregate mean weight diameter slightly decreased with decreasing management intensity. In contrast to absolute POM‐C, fPOM‐C increased in aggregates at both sites with abandonment. Because the oPOM‐C was less affected by abandonment, the ratio of oPOM‐C : fPOM‐C shifted from > 1 to < 1 from meadow to abandoned grassland in aggregates at both sites and thus independent of climate. This suggests that in differently managed mountain grasslands free and occluded POM are functionally different SOM fractions. In bulk soil, the oPOM‐C : fPOM‐C ratio is better suited as an indicator for the response of SOM to management reduction in subalpine grasslands than the total soil C, absolute or relative POM‐C content.     

Factors affecting the molecular structure and mean residence time of occluded organics in a lithosequence of soils under ponderosa pine

Occluded, or intra-aggregate, soil organic matter (SOM) comprises a significant portion of the total C pool in forest soils and often has very long mean residence times (MRTs). However, occluded C characteristics vary widely among soils and the genesis and composition of the occluded organic matter pool are not well understood. This work sought to define the major controls on the composition and MRT of occluded SOM in western U.S. conifer forest soils with specific focus on the influence of soil mineral assemblage and aggregate stability. We sampled soils from a lithosequence of four parent materials (rhyolite, granite, basalt, and dolostone) under Pinus ponderosa. Three pedons were excavated to the depth of refusal at each site and sampled by genetic horizon. After density separation at 1.8 g cm⁻³ into free/light, occluded and mineral fractions, the chemical nature and mean residence time of organics in each fraction were compared. SOM chemistry was explored through the use of stable isotope analyses, ¹³C NMR, and pyrolysis GC/MS. Soil charcoal content estimates were based on ¹³C NMR analyses. Estimates of SOM MRT were based on steady-state modeling of SOM radiocarbon abundance measurements. Across all soils, the occluded fraction was 0.5–5 times enriched in charcoal in comparison to the bulk soil and had a substantially longer MRT than either the mineral fraction or the free/light fraction. These results suggest that charcoal from periodic burning is the primary source of occluded organics in these soils, and that the structural properties of charcoal promote its aggregation and long-term preservation. Surprisingly, aggregate stability, as measured through ultrasonic dispersion, was not correlated with occluded SOM abundance or MRT, perhaps raising questions of how well laboratory measurements of aggregate stability capture the dynamics of aggregate turnover under field conditions. Examination of the molecular characteristics of the occluded fraction was more conclusive. Occluded fraction composition did not change substantially with soil mineral assemblage, but was increasingly enriched in charcoal with depth relative to bulk SOM. Enrichment levels of ¹³C and ¹⁵N suggested a similar degree of microbial processing for the free/light and occluded fractions, and molecular structure of occluded and free/light fractions were also similar aside from charcoal enrichment in the occluded fraction. Results highlight the importance of both fire and aggregate formation to the long-term preservation of organics in western U.S. conifer forests which experience periodic burning, and suggest that the composition of occluded SOM in these soils is dependent on fire and the selective occlusion of charcoal.     

Soil organic matter distribution and microaggregate characteristics as affected by agricultural management and earthworm activity

Stable microaggregates can physically protect occluded soil organic matter (SOM) against decomposition. We studied the effects of agricultural management on the amount and characteristics of microaggregates and on SOM distribution in a marine loam soil in the Netherlands. Three long‐term farming systems were compared: a permanent pasture, a conventional‐arable system and an organic‐arable system. Whole soil samples were separated into microaggregates (53–250 µm), 20–53 µm and < 20 µm organo‐mineral fractions, sand and particulate organic matter, after complete disruption of macroaggregates. Equal amounts of microaggregates were isolated, irrespective of management. However, microaggregates from the pasture contained a larger fraction of total soil organic C and were more stable than microaggregates from the two arable fields, suggesting greater SOM stabilization in microaggregates under pasture. Moreover, differences in the relative contribution of coarse silt (> 20 µm) versus fine mineral particles in the microaggregates of the different management systems demonstrate that different types of microaggregates were isolated. These results, in combination with micromorphological study of thin sections, indicate that the great earthworm activity under permanent pasture is an important factor explaining the presence of very stable microaggregates that are relatively enriched in organic C and fine mineral particles. Despite a distinctly greater total SOM content and earthworm activity in the organic‐ versus the conventional‐arable system, differences in microaggregate characteristics between both arable systems were small. The formation of stable and strongly organic C‐enriched microaggregates seems much less effective under arable conditions than under pasture. This might be related to differences in earthworm species' composition, SOM characteristics and/or mechanical disturbance between pasture and arable land.     

Aggregate-occluded black carbon in soil

The great stability of black carbon (BC) in soils may not be solely attributable to its refractory structure but also to poor accessibility when physically enveloped by soil particles. Our aim was to elucidate the intensity of physical entrapment of BC within soil aggregates. For this purpose, the A horizon of a forest, and of a grassland soil, and of three soils under tillage, were sampled at the experimental station Rotthalmünster, Germany. Black carbon was assessed in water‐stable aggregates and aggregate‐density fractions using benzene polycarboxylic acids as specific markers. The greatest BC concentrations made up 7.2% of organic carbon and were found in the < 53 μm fraction. The smallest BC concentrations occurred in the large macroaggregate fractions (> 2 mm). This pattern has been sustained even after tillage. The C‐normalized BC concentrations were significantly greater (P < 0.05) in the occluded particulate organic matter (OPOM) fractions than in the free particulate organic matter (FPOM) and the mineral fractions. This enrichment of BC compared with organic carbon in the OPOM fractions amounted to factors of 1.5–2.7. Hence, BC was embedded within microaggregates in preference to other organic carbon compounds. Only 2.5–3.5% of BC was located in the OPOM fraction < 1.6 g cm^?3, but 22–24% in the OPOM fraction with a density of 1.6–2.0 g cm^?3. This suggests that BC possibly acted as a binding agent or was selectively enriched during decomposition of protected SOM, or both. Physical inclusion, particularly within microaggregates, could therefore contribute to the long mean‐residence times of soil‐inherent BC.     

Soil organic matter fractions as early indicators for carbon stock changes under different land-use?

With respect to carbon sequestration in soil, attempts have been made to identify soil organic matter (SOM) fractions that respond more rapidly to changes in land-use than bulk SOM, which could thus serve as early indicators for the overall stock change. We used a combination of physical fractionation (size and density separation) and chemical characterisation (C-to-N ratios, CuO lignin signature, ¹³C NMR spectroscopy) to identify sensitive SOM fractions in an agricultural system with sandy dystric cambisols in Bavaria, Germany, 7 years after a land-use change. Land-use types included long-term arable land and grassland, and conversion from one system to the other. Soil carbon and nitrogen contents in 0–3 cm increased from 14 to 39 mg organic carbon g⁻¹ soil, and from 1.7 to 3.9 mg nitrogen g⁻¹ soil in the following order: permanent arable, conversion grassland to arable, conversion arable to grassland, and permanent grassland. Wet sieving and ultrasonic dispersion with 22 J ml⁻¹ released <5% and 60% to 80%, respectively, of the amount of particles >20 μm relative to complete dispersion. The most sensitive fraction, with respect to land-use, was SOM in the fraction >20 μm not released after sequential wet sieving and ultrasonic dispersion. In contrast, the proportion of free light (wet sieving, density <1.8 g cm⁻³) and occluded light (ultrasonic dispersion with 22 J ml⁻¹, <1.8 g cm⁻³) particulate organic matter (POM) showed no clear response to land-use. The structural composition of POM indicated its vegetation origin with a selective enrichment of lignin and a loss of O-alkyl C relative to its plant precursors. Decomposition of the occluded light POM was only slightly advanced relative to the free light POM. In mineral fractions <20 μm, SOM was significantly more transformed than in the coarse fractions, as shown by NMR spectroscopy; however, it revealed no specific land-use pattern. An exception to this was the proportion of O-alkyl C in the clay fraction, which increased with SOC content. Ratios of alkyl to O-alkyl C in mineral fractions <20 μm differentiated samples gave a better differentiation of samples than the C-to-N ratios. We conclude that neither free nor occluded light POM are appropriate early indicators for changes in land-use at the investigated sites; however, total SOM, its distribution with depth, and SOM allocated in stable aggregates >20 μm were more sensitive.     

Effects of polyacrylamide,biopolymer and biochar on the decomposition of 14C‐labelled maize residues and on their stabilization in soil aggregates

The efficacy of applying plant residues to agricultural soils as a carbon (C) source for microorganisms and C sequestration is dependent on soil physiochemical properties, which can be improved by aggregation using soil conditioners. However, no attempt has been made to assess the effects of soil conditioners such as biochar (BC), biopolymer (BP) or polyacrylamide (PAM) on plant residue decomposition. We assessed the effects of BC, synthesized BP and anionic PAM on the decomposition of ¹⁴C‐labelled maize residues and on their stabilization in aggregate fractions in sandy and sandy loam soils. Polyacrylamide and BP were applied at 400 kg ha^?1 and BC was applied at 5000 kg ha^?1, and the soils were incubated for 80 days at 22°C. The conditioners improved the physical and biological properties of both soils, as shown by a 24% increase in the 1–2 mm aggregates. Biochar and BP accelerated the decomposition of plant residues as indicated by ¹⁴CO₂ efflux, and resulted in reduced stabilization of residues in both soils relative to that observed in the control and PAM treatments. The reduction in ¹⁴C incorporation and C stabilization in the BC‐ and BP‐treated soils was observed mainly in the < 0.25‐mm aggregates. This was confirmed by reduction of activity of hydrolytic enzymes (β‐cellobiosidase and β‐glucosidase). Decomposition of plant residues in sandy soil was more sensitive to BP and PAM application than that in sandy loam soil. Improved soil structure after applying BC and BP increased aeration and decreased the contact between plant residues and mineral soil particles and consequently accelerated plant residue decomposition and reduced C sequestration.     

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.     

Qualitative and quantitative differences in particulate organic matter fractions in organic and conventional farming systems

To quantify functionally important differences in soil organic matter (SOM) that result from use of different farming practices, soils from 9 long-term trials comparing manure+legume-based organic, legume-based organic, and conventional farming systems were collected and particulate organic matter (POM) was fractionated to reflect its position within the soil matrix. The free, light POM (FPOM; <1.6 g cm⁻³) not occluded within aggregates and occluded POM (OPOM; <2.0 g cm⁻³) were compared to an undifferentiated POM fraction (coarse fraction, CF; >53 μm) obtained by wet sieving. Fraction C, N, and hydrolyzable N (quantified using the Illinois test (IL-N)) were determined. Organic farming systems had greater quantities of C and N in the OPOM and CF and, greater IL-N contents in all POM fractions considered. The OPOM's C:N ratio (16-19) and was least in the manure+legume-based organic, intermediate in the legume-based organic, and greatest in the conventional systems (P<0.10). Trends in OPOM C:N and IL-N abundance suggested occluded POM was most decomposed, and possibly a greater N reservoir, in the manured soils. The FPOM quality reflected the residues added to each system and its removal improved resolution of quality-based differences in POM associated with long-term management. Subdivision of POM revealed differences in its quality that were not evident using the undifferentiated CF. Quantification of hydrolysable N (IL-N) in POM did not enhance our understanding of management's affect on SOM quality. This multi-site comparison showed organic management simultaneously increased the size of the labile N reservoir and the amount of POM protected within aggregates; and that, occluded POM is more decomposed in manure+legume- than in legume-based organic systems. The characteristics of POM reveal how organic practices improve SOM and suggest the nutrient and substrate decay dynamics of organic systems may differ as a result of the N fertilization strategies they employ.     

Dynamics of soil organic matter associated with particle-size fractions of water-stable aggregates

Stable macroaggregates (> 200 μm) of cultivated soils are reported in the literature to be richer in organic carbon, and in young organic carbon in particular, than microaggregates (< 200 μm). However, the nature of this additional carbon is not yet known. To determine it, we compared the composition of organic matter in stable macroaggregates with that in unstable ones. Macroaggregates 2–3 mm in diameter were separated from two silty cultivated soils from the Paris basin. They were slaked, and the primary particle composition of the resulting fractions was analysed. We used the natural abundance of ¹³C to quantify the amount of young carbon, derived from a maize crop, in the various size fractions. The stable macroaggregates were richer in total C and in young C (younger than 6 and 23 years respectively in the two soils studied) than the unstable ones. This young C comprised 50% particulate organic matter, 20% associated with silt and 30% with clay particles. We propose a schematic composition of aggregates in these soils in which stable aggregates are formed by the binding of microaggregates by additional young organic matter, predominantly plant debris. Young organic matter is preferentially incorporated and is responsible for aggregation, though it is eventually redistributed among aggregate classes through the destruction and re‐formation of the aggregates. We have developed a model to simulate this redistribution. The model shows that stable macroaggregates have a life of a few years, but that microaggregates may exist for decades. We suggest that the stabilization and de‐stabilization of macroaggregates in soils is linked to the incorporation and biodegradation of plant debris.     

Impact of tillage and crop rotation on light fraction and intra-aggregate soil organic matter in two Oxisols

It is well known that no-tillage (NT) practices can promote greater stocks of soil organic matter (SOM) in the soil surface layer compared to conventional tillage (CT) by enhancing the physical protection of aggregate-associated C in temperate soils. However, this link between tillage, aggregation and SOM is less well established for tropical soils, such as Oxisols. The objective of this study was to investigate the underlying mechanisms of SOM stabilization in Oxisols as affected by different crop rotations and tillage regimes at two sites in southern Brazil. Soils were sampled from two agricultural experiment sites (Passo Fundo and Londrina) in southern Brazil, with treatments comparing different crop rotations under NT and CT management, and a reference soil under native vegetation (NV). Free light fraction (LF) and intra-aggregate particulate organic matter (iPOM) were isolated from slaking-resistant aggregates. Of the total C associated with aggregates, 79–90% was found in the mineral fraction, but there were no differences between NT and CT. In contrast, tillage drastically decreased LF-C concentrations in the 0–5 cm depth layer at both sites. In the same depth layer of NT systems at Londrina, the concentrations of iPOM-C were greater when a legume cover crop was included in the rotation. At Londrina, the order of total iPOM-C levels was generally NV > NT > CT in the 0–5 cm depth interval, but the difference between NT and CT was much less than in Passo Fundo. At Passo Fundo, the greatest concentrations and differences in concentrations across tillage treatments were found in the fine (53–250 μm) iPOM fractions occluded within microaggregates. In conclusion, even though no aggregate hierarchy exists in these Oxisols, our results corroborate the concept of a stabilization of POM-C within microaggregates in no-tillage systems, especially when green manures are included in the rotation.     

Distribution and thermal stability of physically and chemically protected organic matter fractions in soils across different ecosystems

Accrual of carbon (C) and nitrogen (N) in soil is a significant and realizable management option to mitigate climate change; thus, a clear understanding of the mechanisms controlling the persistence of C and N in soil organic matter (SOM) across different ecosystems has never been more needed. Here, we investigated SOM distribution between physically and chemically stabilized fractions in soils from a variety of ecosystems (i.e., coniferous and broadleaved forest soils, grassland soils, technosols, and agricultural soils). Using elemental and thermal analyses, we examined changes in the quantity and quality of physically fractionated SOM pools characterized by different mechanisms of protection from decomposition. Independently of the ecosystem type, most of the organic C and total N were found in the mineral-associated SOM pool, known to be protected mainly by chemical mechanisms. Indexes of thermal stability and C/N ratio of this heavy SOM fraction were lower (especially in agricultural soils) compared to light SOM fractions found free or occluded in aggregates, and suggested a marked presence of inherently labile compounds. Our results confirm that the association of labile organic molecules with soil minerals is a major stabilization mechanism of SOM, and demonstrate that this is a generalizable finding occurring across different mineral soils and ecosystems.     

The contribution from hyphae, roots and organic carbon constituents to the aggregation of a sandy loam under long-term clover-based and grass pastures

Water-stable macro-aggregate size fractions (>2.0 mm, 1.0–2.0 mm, 0.5–1.0 mm and 0.25–0.5 mm) and non-aggregated soil from a sandy loam under long-term clover-based pasture and from grass pasture were analysed to determine the role of acid- and water-extractable carbohydrate C, total hyphal length, microbial biomass, organic C and total and mycorrhizal root length in stabilization of the aggregates. Aggregates were examined by scanning electron microscopy (SEM) and the particle-size distribution of the size fractions was also determined. Macro-aggregation increased under grass, relative to clover-based pasture; however, the properties of the aggregate fractions measured did not reflect this difference. Microbial-biomass C, extractable-carbohydrate C, hyphal length, total and mycorrhizal root length and organic C content of the soils were poorly correlated with macro-aggregation. Within the aggregates, the proportion of 250–1000-km sand was smaller and clay, silt and fine sand (20–250 μm) were greater relative to non-aggregated soil, suggesting that the >250-μm sand in the non-aggregated soil limited the stabilization of macro-aggregates. Under SEM, no enmeshment of aggregates by hyphae and roots was apparent. Although 50–160 m hyphae g^?1 soil was found within the aggregates, calculations showed that on average only 5 to 13 lengths of hyphae were associated with each 250-μm cube of soil within the aggregates, and suggested little potential to stabilize the aggregates by enmeshing. On average, all >2.0-mm aggregates contained less than 3.6 mm of roots and less than 50% by weight of <2.0-mm aggregates contained a single length of root. The findings cast doubt about the role of hyphae and fine roots in the stabilization of macro-aggregates through an enmeshing mechanism in sandy soils.     

Soil organic matter distribution as influenced by enchytraeid and earthworm activity

Loam and sandy soils, and the earthworm casts produced with ¹⁴C-labelled plant material in both soils, were incubated in airtight glass vessels with and without enchytraeids to evaluate the effects of soil fauna on the distribution and fragmentation of organic matter. After 1, 3, and 6 weeks, the amount of C mineralised was determined in soils and earthworm casts, and the soil was fractionated into particulate organic matter (POM), the most active pool of soil organic matter, after complete physical dispersion in water. The percentage weight of fine fractions (0-50 µm) was 67.4% in the loam soil. Sand (coarse, i.e. 150-2,000 µm and fine 50-150 µm) represented 87.2% of total weight in sandy soil, while the percentages of C (PC) were 23.2% in coarse POM (2,000-150 µm) and 11.9% in fine POM (150-50 µm). These percentages were higher than those in loam soil, i.e. 3.4% (coarse POM) and 5.4% (fine POM). The PC in coarse POM (9.50%) and fine POM (16.4%) remained higher in casts from sandy soil than in casts from loam soil (4.7% in coarse and 14.3% in fine POM). The highest percentages of ¹⁴C-labelled leaves were found in fine fractions, 55.9% in casts from loam soil and 48.8% in casts from sandy soil. The C mineralisation of the added plant material was higher in casts from the sandy soil (20.3%) than from the loam soil (13.5%). Enchytraeids enhanced C mineralisation in the bulk sandy soil, but did not affect the mineralisation of added plant material in either soil. The main enchytraeid effect was enhancement of the humification process in the bulk sandy soil, the casts from this soil, and the bulk loam soil.     

Different chemical composition of free light,occluded light and extractable SOM fractions in soils of Cerrado and tilled and untilled fields,Minas Gerais,Brazil: a pyrolysis‐GC/MS study

To investigate both the effect of land‐use systems on SOM characteristics and the effect of occlusion in aggregates on chemical composition of the occluded fraction, SOM fractions of soils under Cerrado, no‐tillage and conventional tillage, were investigated. Free light, occluded light and extractable organic matter from native Cerrado and from tilled and untilled fields under maize and bean rotation were separated and chemically analysed by pyrolysis‐GC/MS. Ploughing incorporated more fresh OM into the soil than natural biological activity. Degradation of the occluded light fraction was not fully halted, but was different from that of SOM in the extractable fraction. Recalcitrant compounds had low abundances in the free light and extracted fractions, but were more abundant in the occluded light fraction, where the more accessible compounds were depleted by microbial decomposition. Because of intense decomposition, the extracted fractions did not differentiate between land uses, but differences in the light fractions were significant. The results indicate that the decay of the occluded fraction is different from that of the free light fraction: non‐ideal circumstances of decay caused a relative accumulation of potentially recalcitrant compounds. When considering the rapid turnover of all components in the soil extracts, disruption of aggregates will probably cause rapid decay of the occluded fraction. The distribution of pyrolysis products that can be ascribed to charred wood (polyaromatics) indicates that this fraction is readily decayed if not occluded. Selective decomposition in the occluded fraction may cause a shift in δ¹³C that should not be misinterpreted.     

Clay mineralogy differs qualitatively in aggregate‐size classes: clay‐mineral‐based evidence for aggregate hierarchy in temperate soils

Clay minerals have a major role in soil aggregation because of their large specific surface area and surface charges, which stimulate interactions with other mineral particles and organic matter. Soils usually contain a mixture of clay minerals with contrasting surface properties. Although these differences should result in different abilities of clay minerals regarding aggregate formation and stabilization, the role of different clay minerals in aggregation has been seldom evaluated. In this study, we took advantage of the intrinsic mineral heterogeneity of a temperate Luvisol to compare the role of clay minerals in aggregation. First, grassland and tilled soil samples were separated in water into aggregate‐size classes based on the aggregate hierarchy model. Then, clay mineralogy and organic C in the aggregate‐size classes were analysed. Interstratified minerals containing swelling phases accumulated in aggregated fractions compared with free clay fractions under the two land‐uses. The accumulation increased with decreasing aggregate size from large macroaggregates (> 500 µm) to microaggregates (50–250 µm). Carbon content and carbon‐to‐nitrogen ratio followed the opposite trend. This fully supports the aggregate hierarchy model, which postulates an increasing importance of mineral reactivity in smaller aggregates than in larger aggregates in which the cohesion relies mostly on physical enmeshment by fungal hyphae or small roots. Consequently, differences in the proportion of the different 2:1 clay minerals in soils can influence their structure development. Further research on the links between clay mineralogy and aggregation can improve our understanding of mechanisms of soil resistance to erosion and organic matter stabilization.     

Relative importance of sorption versus aggregation for organic matter storage in subsoil horizons of two contrasting soils

Soil organic matter (OM) stabilization by the mineral phase can take place through sorption and aggregation. In this study we examined both of these processes, (i) organic carbon (OC) sorption onto clay‐sized particles and (ii) OC occlusion in silt‐size aggregates, with the objective of evaluating their relative importance in OM storage and stabilization in soil. We studied two loamy soil profiles (Haplic Luvisol and Plinthic Cambisol) currently under agricultural use down to a depth of 2 m. Our approach was based on two parallel fractionation methods using different dispersion intensities; these methods isolated a free clay fraction (non‐occluded) and a clay fraction occluded within water‐stable silt‐size aggregates. The two clay fractions were analysed for their C content and ¹⁴C activity. The proportion of sorbed OC was estimated as OC loss after hydrofluoric acid (HF) demineralization. Our results showed an important contribution to SOM stabilization by occlusion of OC into silt‐size aggregates with depth through both soil profiles. In the Haplic Luvisol, OC associated with clay and located in silt‐size aggregates accounted for 34–64% of the total soil OC, whereas in the Plinthic Cambisol this occluded material represented 34–40% of total OC. In the Haplic Luvisol, more OC was located in silt‐size aggregates than was sorbed onto clay‐size minerals, suggesting that silt‐size aggregation plays a dominant role in OC storage in this soil. In the Plinthic Cambisol, the abundance of sorbed OC increased with depth and contributed more to the stored C than that associated with silt‐size aggregates. Radiocarbon dating of both clay fractions (either occluded within silt‐size aggregates or not) suggests, in the case of the Plinthic Cambisol, a preferential stabilization of OC within silt‐size aggregates.