运用岩石热解产生的S3和S4信号进行土壤有机质特征研究

Variations in the abundance of soil organic matter（SOM） constituents with different stability have a major impact on important environmental processes, e.g., carbon dioxide（CO2） fluxes between the soil and the atmosphere. Recently, besides the bulk Rock-Eval（RE） data, the mathematical deconvolution of the signals derived from hydrocarbon-like compounds released by thermal cracking of SOM during RE pyrolysis has been increasingly used to estimate the relative contribution of the major SOM classes differing in origin and preservation. This study applied the mathematical deconvolution of the S3 and S4 signals of carbon monoxide（CO） and CO2, produced both by the pyrolysis of the oxygen-containing moieties and by the oxidation of the residual highly resistant organic matter, to characterize the stability of these components. Our results suggested that the stability of the oxygen-containing moieties was controlled by the precursor material and was strongly affected by the land use and the presence of humic substances in the surface horizon of some main soil types in Hungary. In consistence with the bulk RE data, results of the mathematical deconvolution also proved to be diagnostic markers for discriminating the aquatic or terrigenous plants as the main sources of SOM. The mathematical deconvolution of S4 signals derived from the highly resistant SOM fraction allowed us to quantify the contribution of constituents with different stability. Furthermore, the results of this study displayed that the stability of this highly abundant SOM fraction in the surface soil samples depended on source biomass and intensity of leaching.     

Shifts in microbial community and water-extractable organic matter composition with biochar amendment in a temperate forest soil

Biochar amendment in soil has been proposed as a carbon sequestration strategy which may also enhance soil physical and chemical properties such as nutrient and water holding capacity as well as soil fertility and plant productivity. However, biochar may also stimulate microbial activity which may lead to increased soil CO₂ respiration and accelerated soil organic matter (OM) degradation which could partially negate these intended benefits. To investigate short-term soil microbial responses to biochar addition, we conducted a 24 week laboratory incubation study. Biochar produced from the pyrolysis of sugar maple wood at 500 °C was amended at concentrations of 5, 10 and 20 t/ha in a phosphorus-limited forest soil which is under investigation as a site for biochar amendment. The cumulative soil CO₂ respired was higher for biochar-amended samples relative to controls. At 10 and 20 t/ha biochar application rates, the concentration of phospholipid fatty acids (PLFAs) specific to Gram-positive and Gram-negative bacteria as well as actinomycetes were lower than controls for the first 16 weeks, then increased between weeks 16–24, suggesting a gradual microbial adaptation to altered soil conditions. Increases in the ratio of bacteria/fungi and lower ratios of Gram-negative/Gram-positive bacteria suggest a microbial community shift in favour of Gram-positive bacteria. In addition, decreasing ratios of cy17:0/16:1ω7 PLFAs, a proxy used to examine bacterial substrate limitation, suggest that bacteria adapted to the new conditions in biochar-amended soil over time. Concentrations of water-extractable organic matter (WEOM) increased in all samples after 24 weeks and were higher than controls for two of the biochar application rates. Solution-state ¹H NMR analysis of WEOM revealed an increase in microbial-derived short-chain carboxylic acids, lower concentrations of labile carbohydrate and peptide components of soil OM and potential accumulation of more recalcitrant polymethylene carbon during the incubation. Our results collectively suggest that biochar amendment increases the activity of specific microorganisms in soil, leading to increased CO₂ fluxes and degradation of labile soil OM constituents.     

Acid hydrolysis of easily dispersed and microaggregate-derived silt- and clay-sized fractions to isolate resistant soil organic matter

The current paradigm in soil organic matter (SOM) dynamics is that the proportion of biologically resistant SOM will increase when total SOM decreases. Recently, several studies have focused on identifying functional pools of resistant SOM consistent with expected behaviours. Our objective was to combine physical and chemical approaches to isolate and quantify biologically resistant SOM by applying acid hydrolysis treatments to physically isolated silt‐ and clay‐sized soil fractions. Microaggegrate‐derived and easily dispersed silt‐ and clay‐sized fractions were isolated from surface soil samples collected from six long‐term agricultural experiment sites across North America. These fractions were hydrolysed to quantify the non‐hydrolysable fraction, which was hypothesized to represent a functional pool of resistant SOM. Organic C and total N concentrations in the four isolated fractions decreased in the order: native > no‐till > conventional‐till at all sites. Concentrations of non‐hydrolysable C (NHC) and N (NHN) were strongly correlated with initial concentrations, and C hydrolysability was found to be invariant with management treatment. Organic C was less hydrolysable than N, and overall, resistance to acid hydrolysis was greater in the silt‐sized fractions compared with the clay‐sized fractions. The acid hydrolysis results are inconsistent with the current behaviour of increasing recalcitrance with decreasing SOM content: while %NHN was greater in cultivated soils compared with their native analogues, %NHC did not increase with decreasing total organic C concentrations. The analyses revealed an interaction between biochemical and physical protection mechanisms that acts to preserve SOM in fine mineral fractions, but the inconsistency of the pool size with expected behaviour remains to be fully explained.     

A comparison of extraction procedures for water‐extractable organic matter in soils

The characteristics of dissolved organic matter (DOM) in soils are often determined through laboratory experiments. Many different protocols can be used to extract organic matter from soil. In this study, we used five air‐dried soils to compare three extraction methods for water‐extractable organic matter (WEOM) as follows: (i) pressurised hot‐water‐extractable organic carbon (PH‐WEOC), a percolation at high pressure and temperature; (ii) water‐extractable organic carbon (WEOC), a 1‐hour end‐over shaking; and (iii) leaching‐extractable organic carbon (LEOC), a leaching of soil columns at ambient conditions. We quantified the extraction yield of organic carbon; the quality of WEOM was characterized by UV absorbance, potential biodegradability (48‐day incubation) and parallel factor analysis (PARAFAC) modelling of fluorescence excitation emission matrices (FEEMs). Biodegradation of dissolved organic carbon (DOC) was described by two pools of organic C. The proportions of labile and stable DOC pools differed only slightly between the WEOC and LEOC methods, while PH‐WEOC contains more stable DOC. The mineralization rate constants of both labile and stable DOC pools were similar for the three methods. The FEEMs were decomposed into three components: two humic‐like fluorophores and a tryptophan‐like fluorophore. The effect of extraction method was poorly discriminant and the most similar procedures were PH‐WEOC and LEOC while WEOC extracts were depleted in humic‐like fluorophores. This study demonstrates that WEOM quality is primarily determined by soil characteristics and that the extraction method has a smaller, but still significant, impact on WEOM quality. Furthermore, we observed considerable interaction between extraction procedure and soil type, showing that method‐induced differences in WEOM quality vary with soil characteristics.     

Distribution of transformed organic matter in structural units of loamy sandy soddy-podzolic soil

The effect of land use types and fertilizing systems on the structural and aggregate composition of loamy sandy soddy-podzolic soil and the quantitative parameters of soil organic matter has been studied. The contribution of soil aggregates 2–1 mm in size to the total C_org reserve in the humus horizon is higher than the contributions of other aggregates by 1.3–4.2 times. Reliable correlations have been revealed between the contents of total (C_org), labile (C_lab), and active (C₀) organic matter in the soil. The proportion of C₀ is 44–70% of C_lab extractable by neutral sodium pyrophosphate solution. The contributions of each of the 2–1, 0.5–0.25, and <0.25 mm fractions to the total C₀ reserve are 14–21%; the contributions of each of the other fractions are 4–12%. The chemically labile and biologically active components of humic substances reflect the quality changes of soil organic matter under agrogenic impacts. A conceptual scheme has been proposed for the subdivision of soil organic matter into the active, slow (intermediate), and passive pools. In the humus horizon of loamy sandy soddy-podzolic soil, the active, slow, and passive pools contain 6–11, 34–65, and 26–94% of the total C_org, respectively.     

Organic matter in volcanic soils in Chile: Chemical and biochemical characterization

Abstract

Determinations were made of total soil organic matter (SOM), stable and labile organic fractions, biomass carbon (C), and chemical composition of several humus‐soil‐fractions in Chilean volcanic soils, Andosols and Ultisols. Their physico‐chemical properties and humification degree at different stages in edaphic evolution were also assessed. In addition, organic matter models were obtained by chemical and biological syntheses and the structures and properties of natural and synthetic humic materials were compared with SOM. Results indicate that Andosols have higher SOM levels than Ultisols, but the fraction distribution in the latter suggests a shift of the more stable fractions to the more labile ones. Moreover, contents of humines, and humic and fulvic acids suggest that Chilean volcanic soil SOM is highly humified. On the other hand, among the SOM labile fractions, carbohydrate and biomass are about 15% of the SOM which are one of the most important fractions in soil fertility.     

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.     

The priming potential of biochar products in relation to labile carbon contents and soil organic matter status

Recognition of biochar as a potential tool for long-term carbon sequestration with additional agronomic benefits is growing. However, the functionality of biochar in soil and the response of soils to biochar inputs are poorly understood. It has been suggested, for example, that biochar additions to soils could prime for the loss of native organic carbon, undermining its sequestration potential. This work examines the priming potential of biochar in the context of its own labile fraction and procedures for their assessment. A systematic set of biochar samples produced from C4 plant biomass under a range of pyrolysis process conditions were incubated in a C3 soil at three discrete levels of organic matter status (a result of contrasting long-term land management on a single site). The biochar samples were characterised for labile carbon content ex-situ and then added to each soil. Priming potential was determined by a comparison of CO₂ flux rates and its isotopic analysis for attribution of source. The results conclusively showed that while carbon mineralisation was often higher in biochar amended soil, this was due to rapid utilisation of a small labile component of biochar and that biochar did not prime for the loss of native organic soil organic matter. Furthermore, in some cases negative priming occurred, with lower carbon mineralisation in biochar amended soil, probably as a result of the stabilisation of labile soil carbon.     

Analyzing organic matter composition at intact biopore and crack surfaces by combining DRIFT spectroscopy and Pyrolysis‐Field Ionization Mass Spectrometry#

In the clay‐illuvial horizons (Bt) of Luvisols, surfaces of biopores and aggregates can be enriched in clay and organic matter (OM), relative to the bulk of the soil matrix. The OM composition of these coatings determines their bio‐physico‐chemical properties and is relevant for transport and transformation processes but is largely unknown at the molecular scale. The objective of this study was to improve the interpretation of spectra from Fourier transform infrared spectroscopy in diffuse reflectance mode (DRIFT) by using thermograms and released ion intensities obtained with pyrolysis‐field ionization mass spectrometry (Py‐FIMS) for a more detailed analysis of the mm‐scale spatial distribution of OM components at intact structural surfaces. Samples were separated from earthworm burrow walls, crack coatings, uncoated cracks, root channels, and pinhole fillings of the Bt‐horizons of Luvisols. The information from Py‐FI mass spectra enabled the assignment of OM functional groups also from spectral regions of overlapping DRIFT signal intensities to specific OM compound classes. In particular, bands from C=O and C=C bonds in the infrared range of wave numbers between 1,641 and 1,605 cm^?1 were related to heterocyclic N‐compounds, benzonitrile, and naphthalene. The OM at earthworm burrow walls was composed of chemically labile aliphatic C‐rich and rather stable lignin and alkylaromatic compounds whereas the OM of thick crack coatings and pinholes was dominated by heterocyclic N and nitriles and high‐molecular compounds, likely originating from combustion residues. In combination with Py‐FIMS, DRIFT applications to intact samples seem promising for generating a more detailed mm‐scale spatial distribution of OM‐related sorption and wettability properties of crack and biopore surfaces that may serve as preferential flow paths in structured soils.     

Solid-state 13C-NMR dipolar dephasing experiments for quantifying protonated and non-protonated carbon in soil organic matter and model systems

Dipolar dephasing was investigated as a means for quantitatively differentiating protonated and non‐protonated and molecularly mobile and rigid components in soil organic matter. We experimented on cellulose, hemicelluloses, lignin, a protein, chitin, charcoal, palmitic acid and two waxes which served as model systems for components of soil organic matter. Dipolar dephasing decay curves showed significant deviation from the expected exponential decay (for non‐protonated and methyl carbons) and Gaussian decay (for non‐methyl protonated carbons), partly due to rotational and dipolar modulation. No signal is observed for most protonated carbon (excluding methyl carbon) for a dipolar dephasing delay of 45 μs, and so we generated three subspectra, representing non‐protonated, non‐methyl protonated and methyl carbon classes, requiring the acquisition of just the 0‐ and 45‐μs dipolar dephased spectra. This methodology was applied to eight samples of soil organic matter, allowing the determination of relative contributions of overlapping resonances such as C‐substituted and H‐substituted aromatics (110–145 p.p.m.), carbohydrate anomeric and tannin (90–110 p.p.m.), and amino acid and methoxyl (45–65 p.p.m.). The waxes behaved aberrantly, probably because some of their components are highly mobile. We determined accurately the exponential dipolar dephasing decay rates of non‐protonated carbon resonances, free from the interference of rotational and dipolar modulations.     

Impacts of plantation forest management on soil organic matter quality

Purpose  

Light fraction soil organic matter is characterized by rapid mineralization due to the labile nature of its chemical constituents and to the lack of protection by soil colloids. The changes in the size of light fraction soil organic matter constituents are useful early indicators of management-related carbon (C) and nutrient changes. However, previous studies have not assessed the impacts of forest management practices on the chemical composition and sources of organic matter in the light fraction. The change in the chemistry of light fraction soil organic matter may significantly affect turnover rate of organic matter in the whole soil and soil fertility. The aim of this study was to assess how different forest management practices would affect the chemical composition of light fraction soil organic matter.     

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.     

Translocation of soils to stimulate climate change: CO2 emissions and modifications to soil organic matter

The effect of climate change on CO₂ emissions was studied on undisturbed soil monoliths (40‐cm diameter, 25‐cm high), which were translocated to warmer zones than their place of origin. Thirty‐two months after the translocation, a climatic factor deduced from the moisture content of the soil and from the effective mean temperature (temperatures in excess of 5°C) revealed that translocation increased the potential of the climate to enhance the biological processes by between 73% and 26% compared with what the soil would support in its place of origin. At the end of the study, the transported soils had lost a large proportion of both total carbon and nitrogen (between 20 and 45%). During the experiment, the CO₂ emissions from the soils, measured under field conditions, were quite variable, but were usually greater than from soils in situ. The variation in labile C in the soil throughout the experiment was calculated from a first‐order kinetic equation for organic matter decay. The relative CO₂ emissions, expressed in terms of the labile carbon fraction in the soils, were clearly greater in those translocated soils that underwent the most intensive climate change, which indicates that the variations in emissions over time are basically a function of the size of the labile organic matter pool.     

Effect of different management strategies on soil quality of citrus orchards in Southern Italy

Twenty‐six soil samples were collected from 13 paired orchards (organically vs. conventionally managed) homogeneous for age, rootstock and cultivars, belonging to the Eastern Sicily Organic Citrus farm Network. The soil quality was evaluated by chemical and biochemical indicators. The total organic C, humification parameters and isoelectric focusing of extracted organic matter were measured to quantify the size of relevant soil C pools. In addition, C turnover was evaluated by determining microbial C mineralization, C microbial biomass and by calculating the mineralization and metabolic quotient (qCO₂). The results obtained demonstrated that organic citrus soils were characterized by a general increase in all the organic matter pools, which means a greater C supply for soil metabolic processes. This observed trend did not directly influence the organic matter turnover, indicating that the organic approach could act as a soil C‐sink. The soil microflora of organically managed soils showed an improved efficiency in use of energy and organic resources, corresponding to an increased ability of soils under organic management to sustain biological productivity in the long term.     

Land‐use effects on the distribution of soil organic carbon within particle‐size fractions of volcanic soils in the Transmexican Volcanic Belt (Mexico)

The aim of this study was to determine the effect of land‐use and forest cover depletion on the distribution of soil organic carbon (SOC) within particle‐size fractions in a volcanic soil. Emphasis was given to the thermal properties of soils. Six representative sites in Mexico were selected in an area dominated by Andosols: a grassland site, four forested sites with different levels of degradation and an agricultural site. Soils were fractionated using ultrasonic energy until complete dispersion was achieved. The particle‐size fractions were coarse sand, fine sand, silt, clay and particulate organic matter from the coarse sand sized fraction (POM‐CS) and fine sand (POM‐FS). Soil organic carbon decreased by 70% after forest conversion to cropland and long‐term cultivation; forest cover loss resulted in a decrease in SOC of up to 60%. The grassland soil contained 45% more SOC than the cropland one. Soil organic carbon was mainly associated with the silt‐size fraction; the most sensitive fractions to land‐use change and forest cover depletion were POM followed by SOC associated with the silt and clay‐sized fractions. Particulate organic matter can be used as an early indicator of SOC loss. The C lost from the clay and silt‐sized fractions was thermally labile; therefore, the SOC stored in the more degraded forest soils was more recalcitrant (thermally resistant). Only the transformation of forest to agricultural land produced a similar loss of thermally stable C associated with the silt‐sized fraction.     

Long‐term changes of aggregate‐associated and labile soil organic carbon and nitrogen after conversion from forest to grassland and cropland in northern Turkey

Soil management systems can have great effect on soil chemical, physical and biological properties. Conversion of forest to grassland and cropland can alter C and N dynamics. The objective of this study was to evaluate the changes in aggregate‐associated and labile soil organic C and N fractions after conversion of a natural forest to grassland and cropland in northern Turkey. This experiment was conducted on plots subject to three different adjacent land uses (forest, grassland and cropland). Soil samples were taken from 0–5, 5–15 and 15–30 cm depths from each land use. Some soil physical (soil texture, bulk density), chemical (soil pH, soil organic matter, lime content, total organic C and N, inorganic N, free and protected organic C) and biological (microbial biomass C and N, mineralizable C and N) properties were measured. The highest and lowest bulk densities were observed in grassland (1.41 g cm⁻³) and cropland (1.14 g cm⁻³), respectively. Microbial biomass C and total organic C in forest were almost twice greater than grassland and four‐times greater than cropland. Cultivation of forest reduced total organic N, mineralizable N and microbial biomass N by half. The great portion of organic C was stored in macroaggregates (>250 µm) in all the three land uses. Free organic C comprised smaller portion of soil organic C in all the three land uses. Thus, this study indicated that long‐term conversion of forest to grassland and cropland significantly decreased microbial biomass C, mineralizable C and physically protected organic C and the decreases were the greatest in cropland. Copyright © 2011 John Wiley & Sons, Ltd.     

长期施肥对我国典型土壤活性有机质及碳库管理指数的影响

对我国重点农区的6种典型土壤红壤、灰漠土、垆土、潮土、褐土、黑土长期耕作施肥后的活性有机质及碳库管理指数(CMI)进行了研究,探讨施肥对不同土壤活性有机质和CMI的影响。土壤活性有机质用KMnO4氧化法测定,采用3种浓度KMnO4(33、1673、33.mmol/L)将土壤活性有机质分为高活性有机质、中活性有机质和活性有机质3部分。结果表明,只耕作不施肥(CK)10年后土壤活性有机质含量降低,CMI下降11.1～63.6,其中垆土、褐土下降幅度最大、黑土最小。施用化肥也使土壤活性有机质下降,其中单施氮(N)的潮土活性有机质下降最大,达31.3%;化肥配合施用(NPK)的红壤活性有机质下降最大,其余土壤相对较小。施肥使土壤活性有机质和总有机质含量增加,高于初始土壤和CK。施用有机肥或有机肥配施化肥,土壤活性有机质含量和CMI均显著增加,CMI以红壤上升最大,达91.4,潮土最小,仅为4.6。土壤活性有机质的数量及CMI变幅大于土壤总有机质的变化幅度,以CMI变化为大,说明CMI是评价施肥耕作对土壤质量影响的最好指标。土壤活性有机质分组结果表明,红壤活性有机质组成以高活性有机质为主;垆土、灰漠土活性有机质以高活性和中活性两部分为主;潮土以中活性有机质为主。施肥对红壤、灰漠土活性有机质组分影响明显,对垆土、潮土影响相对较小。     

Composition of lipophilic compounds and carbohydrates in the accumulated plant litter and soil organic matter in boreal forests

Carbohydrates and lipophilic compounds constitute an important component of litter and soil organic matter in boreal forests, but are still poorly identified. We characterized needle litter and coarse tree litter (cones, seeds, bark and twigs) from coniferous trees (Pinus sylvestris L. and Picea abies Karst.), and moss litter (Pleurozium schreberi, Hylocomnium speldens), fermentation (F) and humus (H) layers in four boreal forest sites in Finland using a combination of sequential fractionation (non‐polar extractions, NPE; water‐soluble extractions, WSE; acid‐soluble fraction, AS) and detailed analyses on the soluble fractions using GC‐MS. Comparisons among the different layers of the soil organic horizon were used to assess which lipophilic compounds and carbohydrates increased in the F and H layers in proportion to their relative abundance in the litter layer and thus might have a large potential to accumulate in soil organic matter. Both concentrations and relative proportions of different compounds varied among the soil layers. Several of the fatty acids (FAs) found in the litter samples were absent in the F and the H layers. Needle and coarse tree litter contained a wide range of di‐ and triterpenes, but in the F and H layers oxidized forms of dehydroabietic acid and sterols were abundant. The large proportion of dehydroabietic acid in the lipophilic fraction in the H layer suggests that it may be poorly degradable by soil microorganisms, probably because of its anti‐microbial function in trees. The composition of the acid‐soluble fraction indicated that the proportion of cellulose in relation to hemicelluloses increased from the litter layer to the F and H layers. Put together, changes in the relative proportions of organic compounds in soluble fractions indicate that selective preservation of compounds, litter input by plant roots and microbial synthesis of compounds all contribute to the accumulation of aliphatic compounds in the H layer of boreal forests.     

Sources and composition of soil organic matter fractions between and within soil aggregates

It is generally accepted that particulate organic matter derives from plants. In contrast, the enriched labile fraction is thought by many to derive from microbes, especially fungi. However, no detailed chemical characterization of these fractions has been done. In this study, we wanted to assess the sources (plants or microbes; fungi or bacteria) and degree of microbial alteration of (i) three particulate organic matter fractions – namely the free light fraction (1.85 g cm^?3), the coarse (250–2000 μm) and the fine (53–250 μm) intra‐aggregate particulate organic matter fractions – and of (ii) three density fractions of fine‐silt associated carbon – namely < 2.0, 2.0–2.2 (i.e. enriched labile fraction) and > 2.2 g cm^?3– by analysing the amino sugars, by CuO oxidation analyses, and by ¹³C‐, ¹H‐ and ³¹P‐NMR analyses. Macroaggregates (250–2000 μm) were separated by wet‐sieving from a former grassland soil now under a no‐tillage arable regime. The three particulate organic matter fractions and the three density fractions were isolated from the macroaggregates by a combination of density flotation, sonication and sieving techniques. Proton NMR spectroscopy on alkaline extracts showed that the enriched labile fraction is not of microbial origin but is strongly degraded plant material that is enriched in aliphatic moieties partly bound to aromatics. In addition, the enriched labile fraction had a glucosamine content less than the whole soil, indicating that it is not enriched in carbon derived from fungi. Decreasing yields of phenolic CuO oxidation products and increasing side‐chain oxidation in the order coarse intra‐aggregate particulate organic matter < fine inter‐aggregate particulate organic matter < fine‐silt fractions indicate progressive alteration of lignin as particle size decreases. The light fraction was more decomposed than the coarse inter‐aggregate particulate organic matter, as indicated by (i) its larger ratio of acid‐to‐aldehyde of the vanillyl units released by CuO oxidation, (ii) the smaller contribution of H in carbohydrates to total extractable H as estimated by ¹H‐NMR spectroscopy, and (iii) a larger contribution of monoester P to total extractable P in the ³¹P‐NMR spectra. In conclusion, the four fractions are derived predominantly from plants, but microbial alteration increased as follows: coarse inter‐aggregate particulate organic matter < light fraction ≈ fine inter‐aggregate particulate organic matter < enriched labile fraction.     

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.