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.     

Calibration model of microbial biomass carbon and nitrogen concentrations in soils using ultraviolet absorbance and soil organic matter

There is a need for a rapid, simple and reliable method of determining soil microbial biomass (SMB) for all soils because traditional methods are laborious. Earlier studies have reported that SMB‐C and ‐N concentrations in grassland and arable soils can be estimated by measurement of UV absorbance in soil extracts. However, these previous studies focused on soils with small soil organic matter (SOM) contents, and there was no consideration of SOM content as a covariate to improve the estimation. In this study, using tropical and temperate forest soils with a wide range of total C (5–204 mg C g^?1 soil) and N (1–12 mg N g^?1 soil) contents and pH values (4.1–5.9), it was found that increase in UV absorbance of soil extracts at 280 nm (UV₂₈₀) after fumigation could account for 92–96% of the variance in estimates of the SMB‐C and ‐N concentrations measured by chloroform fumigation and extraction (P < 0.001). The data were combined with those of earlier workers to calibrate UV‐based regression models for all the soils, by taking into account their varying SOM content. The validation analysis of the calibration models indicated that the SMB‐C and ‐N concentrations in the 0–5 cm forest soils simulated by using the increase in UV₂₈₀ and SOM could account for 86–93% of the variance in concentrations determined by chloroform fumigation and extraction (P < 0.001). The slope values of linear regression equations between measured and simulated values were 0.94 ± 0.03 and 0.94 ± 0.04, respectively, for the SMB‐C and ‐N. However, simulation using the regression equations obtained by using only the data for forest profile soils gave less good agreement with measured values. Hence, the calibration models obtained by using the increase in UV₂₈₀ and SOM can give a rapid, simple and reliable method of determining SMB for all soils.     

Soil organic matter dynamics and land use change at a grassland/forest ecotone

In the grassland/forest ecotone of North America, many areas are experiencing afforestation and subsequent shifts in ecosystem carbon (C) stocks. Ecosystem scientists commonly employ a suite of techniques to examine how such land use changes can impact soil organic matter (SOM) forms and dynamics. This study employs four such techniques to compare SOM in grassland (Bromus inermis) and recently forested (∼35 year, Ulmus spp. and Quercus spp.) sites with similar soil types and long-term histories in Kansas, USA. The work examines C and nitrogen (N) parameters in labile and recalcitrant SOM fractions isolated via size and density fractionation, acid hydrolysis, and long-term incubations. Size fractionation highlighted differences between grassland and forested areas. N concentration of forested soils’ 63-212 μm fraction was higher than corresponding grassland soils’ values (3.0±0.3 vs. 2.3±0.3 mg g_fraction⁻¹, P<0.05), and N concentration of grassland soils’ 212-2000 μm fraction was higher than forested soils (3.0±0.4 vs. 2.3±0.2 mg g_fraction⁻¹, P<0.05). Similar trends were observed for these same fractions for C concentration; forested soils exhibited 1.3 times the C concentration in the 63-212 μm fraction compared to this fraction in grassland soils. Fractions separated via density separation and acid hydrolysis exhibited no differences in [C], [N], δ¹⁵N, or δ¹³C when compared across land use types. Plant litterfall from forested sites possessed significantly greater N concentrations than that from grassland sites (12.41±0.10 vs. 11.62±0.19 mg g_litter⁻¹). Long-term incubations revealed no differences in C or N dynamics between grassland and forested soils. δ¹³C and δ¹⁵N values of the smallest size and the heavier density fractions, likely representing older and more recalcitrant SOM, were enriched compared to younger and more labile SOM fractions; δ¹⁵N of forested soils’ 212-2000 μm fraction were higher than corresponding grassland soils (1.7±0.3‰ vs. 0.5±0.4‰). δ¹³C values of acid hydrolysis fractions likely reflect preferential losses of ¹³C-depleted compounds during hydrolysis. Though C and N data from size fractions were most effective at exhibiting differences between grassland and forested soils, no technique conclusively indicates consistent changes in SOM dynamics with forest growth on these soils. The study also highlights some of the challenges associated with describing SOM parameters, particularly δ¹³C, in SOM fractions isolated by acid hydrolysis.     

Soil microbial biomass and activity: the effect of site characteristics in humid temperate forest ecosystems

Microbial biomass, respiratory activity, and in‐situ substrate decomposition were studied in soils from humid temperate forest ecosystems in SW Germany. The sites cover a wide range of abiotic soil and climatic properties. Microbial biomass and respiration were related to both soil dry mass in individual horizons and to the soil volume in the top 25 cm. Soil microbial properties covered the following ranges: soil microbial biomass: 20 µg C g^–1–8.3 mg C g^–1 and 14–249 g C m^–2, respectively; microbial C–to–total organic C ratio: 0.1%–3.6%; soil respiration: 109–963 mg CO₂‐C m^–2 h^–1; metabolic quotient (qCO₂): 1.4–14.7 mg C (g C_mic)^–1 h^–1; daily in‐situ substrate decomposition rate: 0.17%–2.3%. The main abiotic properties affecting concentrations of microbial biomass differed between forest‐floor/organic horizons and mineral horizons. Whereas microbial biomass decreased with increasing soil moisture and altitude in the forest‐floor/organic horizons, it increased with increasing N_tot content and pH value in the mineral horizons. Quantities of microbial biomass in forest soils appear to be mainly controlled by the quality of the soil organic matter (SOM), i.e., by its C : N ratio, the quantity of N_tot, the soil pH, and also showed an optimum relationship with increasing soil moisture conditions. The ratio of C_mic to C_org was a good indicator of SOM quality. The quality of the SOM (C : N ratio) and soil pH appear to be crucial for the incorporation of C into microbial tissue. The data and functional relations between microbial and abiotic variables from this study provide the basis for a valuation scheme for the function of soils to serve as a habitat for microorganisms.     

Influence of geogenic CO2 on mineral and organic soil constituents on a mofette site in the NW Czech Republic

Geogenic CO₂ emission on mofette sites may be a factor in soil formation. To demonstrate a CO₂ effect, we studied soils (0–60 cm depth) along a transect across a mofette in the NW Czech Republic. We determined CO₂ partial pressures (p(CO₂)), and the contents in the soil of carbon (C), nitrogen (N), sulphur and dithionite‐ and oxalate‐extractable iron and manganese. X‐ray diffractometry (XRD) and Fourier‐transform infrared (FTIR) spectroscopy methods were applied to the soils' particle‐size fractions. The CO₂ partial pressures varied considerably (0.001–1) along the transect and were positively correlated with both the C_org contents (5.5–432.9 g kg⁻¹) and the C:N ratio (9.3–32.2), indicating a decreased turnover of organic parent material with increasing CO₂. When the soil atmosphere was entirely composed of CO₂, pedogenic Fe oxide contents were small (minimum 0.5 g dithionite‐extractable Fe kg⁻¹) and poorly crystalline. XRD and FTIR spectroscopy revealed primary and secondary minerals such as quartz, feldspars, mica, illite, kaolinite and halloysite irrespective of CO₂ contents. A pronounced effect of CO₂ was found for soil organic matter (SOM), because the FTIR spectra did not reveal a normal accumulation of alkyl C and lipids of microbial origin in the clay fraction. This indicates that microbial synthesis and/or degradation of plant‐derived aliphatic species were reduced. We did not detect more organo–mineral associations, microbially formed polypeptides or pectin in clay fractions in comparison with the clay‐plus‐silt fractions at large p(CO₂). This indicates relatively unaltered particulate OM in the clay fraction. At large p(CO₂) values, the IR bands indicative of lignin became detectable and that of aryl ketones in lignin was positively correlated with p(CO₂). Thus, we suggest that microbial formation of SOM and degradation of lignin is restricted under an increased CO₂ atmosphere. We attribute less humification at increased CO₂ in the soil atmosphere to a decrease in oxidative transformations and decreased microbial activity.     

Characteristic alterations of quantity and quality of soil organic matter caused by forest fires in continental Mediterranean ecosystems: a solid-state 13C NMR study

The variable effect of different types of forest fires on the quantity and quality of soil organic matter (SOM) was analysed by comparing burnt and unburnt soils from six forest ecosystems in central Spain by organic elemental analysis and solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Whole soil samples were collected 1 to 2 years after the fires and included one site affected by two fires within 2 years. The fire‐affected soils showed no common pattern with respect to the amount of additional carbon (C_add) but at all sites, the fire enhanced the aromatic‐C content. The weakest fire intensity resulted in the greatest aromatic‐C enrichment factor, EF_{I(aromatic C)} indicating the greatest local accumulation of char. The respective C_add disclosed an EF_{I(aromatic C)} to EF_{I(alkyl C)} ratio, B_char, of c.1, which supports a small degree of charring. Extensive combustion and volatilization at stronger fire intensities yielded a decrease of EF_{I(aromatic C)} and an increase in B_char. These trends are in good agreement with fire intensity and forest fuel combustibility in the various sites and therefore these indices could be used to elucidate the quality and quantity of char input that occurs during and after forest fires. No ¹³C NMR evidence for substantial inputs from non‐charred plant necromass was found for any of the single‐burn soils. The large carboxyl‐C content of C_add is evidence of the occurrence of oxidation reactions very shortly after the fire. In comparing the single and double‐burn sites, no additional char input was observed for the double‐burn site, possibly because of complete combustion of young shrubs and char remains during the second fire. The large O‐alkyl‐C portion found in C_add of the double‐burn soil is best explained by decreased litter degradation.     

Turnover and availability of soil organic carbon under different Mediterranean land‐uses as estimated by 13C natural abundance

Soil organic matter (SOM) is an important factor in ecosystem stability and productivity. This is especially the case for Mediterranean soils suffering from the impact of human degradation as well as harsh climatic conditions. We used the carbon (C) exchange resulting from C₃‐C₄ and C₄‐C₃ vegetation change under field conditions combined with incubations under controlled conditions to evaluate the turnover and availability of soil organic C under different land‐uses. The 40‐year succession of Hyparrenia hirta L. (C₄ photosynthesis) after more than 85 years of olive tree (Olea europaea L.; C₃ photosynthesis) growth led to the exchange of 54% of soil organic C from C₃ to C₄ forms. In contrast, 21 years of vine (Vitis vinifera L.) growing after H. hirta decreased the organic C content to 57%. Considering this exchange and decrease as well as the periods after the land‐use changes, we calculated the mean residence time (MRT) of soil C of different ages. The MRT of C under grassland dominated by H. hirta was about 19 years, but was 180 years under the vineyard. The rates of C accumulation under the H. hirta grassland were about 0.36 Mg C ha^?1 year^?1. In contrast, the rates of C losses after conversion from natural grassland to a vineyard were 1.8 times greater and amounted to 0.65 Mg C ha^?1 year^?1. We conclude that changes of land use from natural Mediterranean grassland to a vineyard lead to very large C losses that cannot be compensated for over the same periods.     

Gross N transformation rates and net N mineralisation rates related to the C and N contents of soil organic matter fractions in grassland soils of different age

We investigated the relationship between soil organic matter (SOM) content and N dynamics in three grassland soils (0-10 and 10-20 cm depth) of different age (6, 14 and 50 y-old) with sandy loam textures. To study the distribution of the total C and N content the SOM was fractionated into light, intermediate and heavy density fractions of particulate macro-organic matter (150-2000 μm) and the 50-150 μm and <50 μm size fractions. The potential gross N transformation rates (mineralisation, nitrification, NH₄⁺ and NO₃⁻ immobilization) were determined by means of short-term, fully mirrored ¹⁵N isotope dilution experiments (7-d incubations). The long-term potential net N mineralisation and gross N immobilization rates were measured in 70-d incubations. The total C and N contents mainly tended to increase in the 0-10 cm layer with increasing age of the grassland soils. Significant differences in total SOM storage were detected for the long-term (50 y-old) conversion from arable land to permanent grassland. The largest relative increase in C and N contents had occurred in the heavy density fraction of the macro-organic matter, followed by the 50-150 and <50 μm fractions. Our results suggest that the heavy density fraction of the macro-organic matter could serve as a good indicator of early SOM accumulation, induced by converting arable land to permanent grassland. Gross N mineralisation, nitrification, and (long-term) gross N immobilization rates tended to increase with increasing age of the grasslands, and showed strong, positive correlations with the total C and N contents. The calculated gross N mineralisation rates (7-d incubations) and net N mineralisation rates (70-d incubations) corresponded with a gross N mineralisation of 643, 982 and 1876 kg N ha⁻¹ y⁻¹, and a net N mineralisation of 195, 208 and 274 kg N ha⁻¹ y⁻¹ in the upper 20 cm of the 6, 14 and 50 y-old grassland soils, respectively. Linear regression analysis showed that 93% of the variability of the gross N mineralisation rates could be explained by variation in the total N contents, whereas total N contents together with the C-to-N ratios of the <50 μm fraction explained 84% of the variability of the net N mineralisation rates. The relationship between long-term net N mineralisation rates and gross N mineralisation rates could be fitted by means of a logarithmic equation (net m=0.24Ln(gross m)+0.23, R²=0.69, P<0.05), which reflects that the ratio of gross N immobilization-to-gross N mineralisation tended to increase with increasing SOM contents. Microbial demand for N tended to increase with increasing SOM content in the grassland soils, indicating that potential N retention in soils through microbial N immobilization tends to be limited by C availability.     

NaOH‐extractable organic matter of andic soils from Galicia (NW Spain) under different land use regimes: a pyrolysis GC/MS study

The objective of this study was to determine to what extent the attenuation or loss of andic soil properties caused by land use change – from forest (FOR, average C content 118.2 ± 23.7 g kg^?1) to agricultural land (AGR, average C content 55.7 ± 16.7 g kg^?1) use – is reflected in soil organic matter (SOM) at the molecular level. For this, NaOH‐extractable SOM of A horizons from 17 soils developed on amphibolitic parent material in NW Spain was studied by pyrolysis gas chromatography spectrometry (Py‐GC/MS). We also included two buried andic A horizons (PAL, 2200 cal yr BP in age) on the same parent material, as a reference for the molecular composition of SOM from soils without recent litter additions. Organic matter of PAL soils had a composition largely different from that of superficial soils (FOR and AGR), with an important relative contribution of microbial polysaccharides and N‐compounds, and an absence of compounds that characterize fresh plant litter (e.g. lignins). In the superficial soils, the relative contribution of lignin‐derived compounds was greater in AGR than in FOR soils. Differences were also observed in the relative contribution of aliphatic compounds, FOR soils being enriched in this type of components compared with AGR soils. The results indicated that land use change from FOR to AGR, which was accompanied by a decrease in total SOM, resulted in an enrichment in primary SOM. The smaller relative abundance of primary SOM derivatives in andic FOR soils indicates that these compounds were quickly degraded in Andisols.     

Post-harvest residue management effects on recalcitrant carbon pools and plant biomarkers within the soil heavy fraction in Pinus radiata plantations

Forest soils contain about 30% of terrestrial carbon (C) and so knowledge of the influence of forest management on stability of soil C pools is important for understanding the global C cycle. Here we present the changes of soil C pools in the 0-5 cm layer in two second-rotation Pinus radiata (D.Don) plantations which were subjected to three contrasting harvest residue management treatments in New Zealand. These treatments included whole-tree harvest plus forest floor removal (defined as forest floor removal hereafter), whole-tree, and stem-only harvest. Soil samples were collected 5, 10 and 15 years after tree planting at Kinleith Forest (on sandy loam soils) and 4, 12 and 20 years after tree planting at Woodhill Forest (on sandy soils). These soils were then physically divided into light (labile) and heavy (stable) pools based on density fractionation (1.70 g cm⁻³). At Woodhill, soil C mass in the heavy fraction was significantly greater in the whole-tree and stem-only harvest plots than the forest floor removal plots in all sampling years. At Kinleith, the soil C mass in the heavy fraction was also greater in the stem-only harvest plots than the forest floor removal plots at year 15. The larger stable soil C pools with increased residue return was supported by analyses of the chemical composition and plant biomarkers in the soil organic matter (SOM) heavy fractions using NMR and GC/MS. At Woodhill, alkyl C, cutin-, suberin- and lignin-derived C contents in the SOM heavy fraction were significantly greater in the whole-tree and stem-only harvest plots than in the forest floor removal plots in all sampling years. At Kinleith, alkyl C (year 15), cutin-derived C (year 5 and 15) and lignin-derived C (Year 5 and 10) contents in the SOM heavy fraction were significantly greater in stem-only harvest plots than in plots where the forest floor was removed. The analyses of plant C biomarkers and soil δ¹³C in the light and heavy fractions of SOM indicate that the increased stable soil C in the heavy fraction with increased residue return might be derived from a greater input of recalcitrant C in the residue substrate.     

森林生态系统中土壤有机质组分的固态13C核磁共振波谱表征

Forest management practices such as prescribed burning and thinning in forest ecosystems may alter the properties of soil organic matter (SOM).In this study,surface soils from field plots in the Bankhead National Forest,Alabama,USA,were used to investigate possible SOM transformations induced by thinning and burning.Elemental analysis and solid-state 13C cross polarization magic angle spinning nuclear magnetic resonance (13C CPMAS NMR) spectroscopy were used to characterize SOM fractions in whole soils,humic substances,and density fractions.Our data revealed that the changes in SOM fractions due to the repeated burning carried out in the forest ecosystem studied were involved mainly with alkyl C,O-alkyl C,and carbohydrate functional groups,implying that most prominent reactions that occurred involved dehydrogenation,de-oxygenation,and decarboxylation.In addition,burning and thinning might have also affected the distribution and composition of free and occluded particulate SOM fractions.The limited structural changes in SOM fractions suggested that low-intensity prescribed fire in the forest ecosystem studied will not create major structural changes in SOM fractions.     

Long-term cultivation effects on the quantity and quality of organic matter in selected Canadian prairie soils

Sixteen Orthic Chernozemic surface soil samples, one half from virgin prairie and one half from adjacent cultivated prairie (cultivated for 31 to 94 years), were collected from eight sites throughout Southern Saskatchewan, Canada. Samples were analyzed for total organic C and a number of other chemical and physical properties. The virgin and cultivated soils at site No. 4 were selected for more detailed analysis by CP-MAS ¹³C NMR, Curie-point-pyrolysis-gas chromatography/mass spectrometry (Cp-Py-GC/MS), and by pyrolysis-field ionization mass spectrometry (Py-FIMS). Long-term cultivation resulted in large significant decreases in total SOM (soil organic matter), as represented by total soil organic C. There were significant increases in aromaticity of the SOM as a result of long-term cultivation as indicated by CP-MAS ¹³C NMR spectroscopy. This was mainly attributable to the result of cultivation-enhanced degradation of aliphatic C relative to aromatic C. Organic compounds identified in the Cp-Py-GC/MS spectra of the virgin and cultivated soils at site No. 4 consisted of n-alkanes (ranging from C₁₁ to C₂₂) and alkenes (ranging from C_7:1 to C_21:1), with the virgin soil being richer in alkenes than the cultivated soil. Other components identified were cyclic aromatics, carbocyclics, N-containing aromatics, N-heterocyclics, benzene and substituted benzenes, phenols and substituted phenols and substituted furans. The compounds identified appeared to originate from long-chain aliphatics, lignins, polyphenols, aromatics, polysaccharides, and N-containing compounds in the two soils. While qualitatively similar compounds were identified by Py-FIMS in the two soils, the total ion intensity (TII) of the virgin soil was almost 2.5 times as high as that of the cultivated soil. This suggests that cultivation made the organic matter less volatile, either by favouring the formation of higher molecular weight organic matter or by promoting the formation of non-volatile metal-organic matter complexes. The Py-FIMS spectra showed that the virgin soil contained relatively more lignin dimers, lipids, sterols, and n-C₁₆ to n-C₃₄ fatty acids than the cultivated soil. Thus, conversely, the cultivated soil was richer in carbohydrates, phenols and lignin monomers, alkyl aromatics and N-containing compounds, including peptides, than the virgin soil.     

Soil organic matter transformations induced by Hieracium pilosella L. in tussock grassland of New Zealand

 To study the effect of Hieracium pilosella L. invasion on the transformations of soil organic matter of New Zealand tussock grassland soils (Ustochrepts), plant material and soils underneath Hieracium, the surrounding halo, and the adjacent herbfield (depleted tussock grassland) were examined for their chemical composition. An attempt was made to reveal possible changes in chemical composition of the soil organic matter induced by H. pilosella invasion. Small differences were detected by solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy in the composition of the plant and soil materials from these zones. Most of the differences in soil organic matter occurred due to differences in the amount and quality of plant-residue inputs. Comparable amounts of phenolic C were detected in the solid-state ¹³C NMR spectra of H. pilosella and herbfield vegetation, while alkaline CuO oxidation yielded considerable lower lignin oxidation products for H. pilosella. A slightly higher proportion of these compounds in H. pilosella soil revealed an accumulation and a low degradation rate of lignin compounds under H. pilosella. The HCl hydrolysis and solid-state ¹⁵N NMR spectroscopy showed similar chemical compositions of the N fractions of the three different soils. The absence of ¹⁵N NMR signal intensity assignable to aniline derivatives or aromatic heterocyclic N indicates that the condensation of phenolic compounds with N groups plays a minor role in N sequestration in these soils. Received: 6 September 1999     

Soil organic carbon stocks,distribution, and composition affected by historic land use changes on adjacent sites

Historic alterations in land use from forest to grassland and cropland to forest were used to determine impacts on carbon (C) stocks and distribution and soil organic matter (SOM) characteristics on adjacent Cambisols in Eastern Germany. We investigated a continuous Norway spruce forest (F-F), a former cropland afforested in 1930 (C-F), and a grassland deforested in 1953 (F-G). For C and N stocks, we sampled the A and B horizons of nine soil pits per site. Additionally, we separated SOM fractions of A and B horizons by physical means from one central soil pit per pedon. To unravel differences of SOM composition, we analyzed SOM fractions by ¹³C-CPMAS NMR spectroscopy and radiocarbon analysis. For the mineral soils, differences in total C stocks between the sites were low (F-F = 8.3 kg m⁻²; C-F = 7.3 kg m⁻²; F-G = 8.2 kg m⁻²). Larger total C stocks (+25%) were found under continuous forest compared with grassland, due to the C stored within the organic horizons. Due to a faster turnover, the contents of free particulate organic matter (POM) were lower under grassland. High alkyl C/O/N-alkyl C ratios of free POM fractions indicated higher decomposition stages under forest (1.16) in relation to former cropland (0.48) and grassland (0.33). Historic management, such as burning of tree residues, was still identifiable in the subsoils by the composition and ¹⁴C activity of occluded POM fractions. The high potential of longer lasting C sequestration within fractions of slower turnover was indicated by the larger amounts of claybound C per square meter found under continuous forest in contrast to grassland.     

Quantification of long‐chain fatty acids in dissolved organic matter and soils

The objective was to develop and adapt a versatile analytical method for the quantification of solvent extractable, saturated long‐chain fatty acids in aquatic and terrestrial environments. Fulvic (FA) and humic (HA) acids, dissolved organic matter (DOM) in water, as well as organic matter in whole soils (SOM) of different horizons were investigated. The proposed methodology comprised extraction by dichloromethane/acetone and derivatization with tetramethylammonium hydroxide (TMAH) followed by gas chromatography/mass spectrometry (GC/MS) and library searches. The C_10:0 to C_34:0 methyl esters of n‐alkyl fatty acids were used as external standards for calibration. The total concentrations of C_14:0 to C_28:0 n‐alkyl fatty acids were determined in DOM obtained by reverse‐osmosis of Suwannee river water (309.3 μg g^—1), in freeze‐dried brown lake water (180.6 μg g^—1), its DOM concentrate (93.0 μg g^—1), humic acid (43.1 μg g^—1), and fulvic acid (42.5 μg g^—1). The concentrations of the methylated fatty acids (n‐C_16:0 to n‐C_28:0) were significantly (r² = 0.9999) correlated with the proportions of marker signals (% total ion intensity (TII), m/z 256 to m/z 508) in the corresponding pyrolysis‐field ionization (FI) mass spectra. The concentrations of terrestrial C_10:0 to C_34:0 n‐alkyl fatty acids from four soil samples ranged from 0.02 μg g^—1 to 11 μg g^—1. The total concentrations of the extractable fatty acids were quantified from a Podzol Bh horizon (26.2 μg g^—1), Phaeozem Ap unfertilized (48.1 μg g^—1), Phaeozem Ap fertilized (57.7 μg g^—1), and Gleysol Ap (66.7 μg g^—1). Our results demonstrate that the method is well suited to investigate the role of long‐chain fatty acids in humic fractions, whole soils and their particle‐size fractions and can be serve for the differentiation of plant growth and soil management.     

Effect of soil pH on the chemical composition of organic matter in physically separated soil fractions in two broadleaf woodland sites at Rothamsted,UK

Although acid soils are common in forest ecosystems, and there is documented evidence of pH influencing transformations of organic matter in soil, there are surprisingly few studies on the influence of soil pH on the chemical structure of physically fractionated soil organic matter (SOM). The aim of this study was to characterize the influence of pH on the chemical and physical processes involved in SOM stabilization. Forest soils of different pH (4.4 and 7.8) sampled from two long‐term experiments at Rothamsted Research (UK) were physically fractionated. The free light fraction (FLF), the intra‐aggregate light fraction and the fine silt and clay (S + C, <25 µm) were characterized using elemental, isotopic (δ¹³C), thermogravimetric, differential thermal, diffuse reflectance infrared Fourier transform spectroscopy and high‐resolution magic angle spinning ¹H nuclear magnetic resonance analyses. The quantitative distribution of carbon (C) between SOM fractions differed between the two soils. Carbon contents in the light fractions from the acid soil were significantly greater than in those of the alkaline soil. In contrast, in S + C fractions, C content was greater in the alkaline soil. FLF from the acid soil was characterized by a greater C:N ratio, smaller δ¹³C and greater content of thermo‐labile compounds compared with FLF from the alkaline soil. In contrast, there was only a weak effect of soil pH on the chemical composition of the organic matter in S + C fractions. Irrespective of soil pH, these latter fractions contained mainly aliphatic compounds such as carbohydrates, carboxylic acid, amide and peptide derivates. This suggested that physical mechanisms, involving the interactions between SOM and mineral surfaces, are of greater importance than the presence of chemically recalcitrant species in protecting SOM associated with the finest soil fractions.     

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 fate of soyabean photosynthetic carbon varies in Mollisols differing in organic carbon

The fate of photosynthetically‐fixed carbon (C) in the plant–soil–microbe continuum has received much interest because of its relevance to soil C and the global C cycle. However, information on the flow of this plant C below ground and its contribution to soil C sequestration in soils with contrasting organic C (C_org) is limited. In this study, soyabean (Glycine max L. Merr.) was grown in three Mollisols with low (1.04%), medium (2.90%) and high (5.05%) C_org, respectively. Plants were labelled with ¹³CO₂ to trace the photosynthetic C dynamics in the plant–soil system for up to 288 hours. The total amount of net fixed ¹³C by plants ranged from 66 to 78 mg pot^?1, and there was no difference between soils. The amount of ¹³C in soil organic matter (SOM) increased from 1.9 to 6.1 mg pot^?1 over time in the high‐C_org soil, while it showed a non‐significant change with 2.2 mg pot^?1 (on average) in the medium‐C_org soil, and decreased from 2.9 to 0.1 mg pot^?1 in the low‐C_org soil. In the low‐C_org soil, the amount of ¹³C in soil microbes decreased markedly over time, showing a fast turnover, and had a significant correlation (P ≤ 0.01) with ¹³C in the SOM pool. However, such a relationship was not significant in the soil with high or medium C_org. These results indicate that most of the root‐derived C in the low‐C_org soil is degraded quickly by microbial activity, while the greater input of the photosynthetic C to SOM in the high‐ and/or medium‐C_org soil can probably be attributed to physical sorption of root‐derived C by SOM and minerals, thus protecting it against microbial decomposition.     

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.     

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.