Long-term effects of crop rotation and fertilization on soil organic matter composition

Long‐term effects of crop rotation and fertilization are mostly observed with respect to the amount of soil organic matter (SOM) and measured in terms of soil organic carbon (SOC). In this paper, we analyze the SOM composition of samples from long‐term agricultural field experiments at sandy and clayey sites that include complex crop rotations and farm‐yard manure applications. The organic matter (OM) composition of the soil samples, OM(Soil), and that of sequentially extracted water, OM(W), and sodium pyrophosphate, OM(PY), soluble fractions was analyzed using Fourier Transform Infrared Spectroscopy (FTIR). The fraction OM(PY) represented between 13 and 34% of SOC, about 10 times that of OM(W). Site specific differences in OM(Soil) composition were larger than those between crop rotations and fertilizer applications. The smaller C=O group content in FTIR spectra of OM(W) compared with OM(PY) suggests that analysis of the more stable OM(PY) fraction is preferable over OM(W) or OM(Soil) for identifying long‐term effects, the OM(Soil) and OM(W) fractions and the content of CH groups being less indicative. Farm‐yard manure application leads to a more similar content of C=O groups in OM(PY) between crop rotations and fertilizer plots at both sites. Short‐term effects from soil tillage or potato harvesting on composition of OM require further studies.     

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.     

Impact of Acacia auriculiformis on the chemical fertility of sandy soils on the Batéké plateau,D.R. Congo

A 17‐year chronosequence of Acacia auriculiformis fallows on Arenosols of the Batéké Plateau (D.R. Congo) was surveyed and compared with virgin savannah soils to assess chemical soil fertility changes induced by these N‐fixing trees. Significant increases in organic carbon content, total nitrogen content, cation exchange capacity and sum of base cations were found after relatively short fallow periods of only 4 years and did not only affect the forest floor, but extended to at least 50 cm depth. The Acacia act as a major source of organic matter (OM), hence increasing organic carbon and nitrogen content and decreasing the C/N ratio. The increased OM content suggests that humification processes are the main cause of the significant decrease in pH. Total exchangeable cations initially increased slowly but doubled (topsoil 0–25 cm) and tripled (subsoil 25–50 cm) after 10 years. The point of zero net proton charge was systematically lower than soil pH and decreased with increasing OM content, thereby increasing the cation exchange capacity, although concurrent acidification retarded a significant beneficial impact at field pH on Acacia fallows of 10 years and older. Although the chemical soil fertility improves steadily with time, after 8 years of Acacia fallow the absolute amounts of available nutrients are still small and slash and burn practices are required to liberate the nutrients stored in the remaining biomass and litter before each new cropping period.     

Cation treatment and drying‐temperature effects on nonylphenol and phenanthrene sorption to a sandy soil

The objective of this study was to investigate the effects of mono‐ and polyvalent cations on sorption of the two hydrophobic compounds nonylphenol (NP) and phenanthrene (Phe). To this end, exchange sites of a sandy soil were saturated with either Na⁺, Ca²⁺, or Al³⁺ and excess salts were removed by washing. The samples were then sterilized and either stored moist, dried at room temperature, or at 20°C, 60°C, or 105°C in a vented oven. Saturation with Na⁺ led to an increase of dissolved organic C (DOC) concentration in the soil water extracts, whereas the polyvalent cations Ca²⁺ and Al³⁺ decreased it. The ¹H‐NMR relaxometry analyses showed that Al³⁺ restricted the mobility of water molecules that are confined within the SOM structure to a higher extent than Ca²⁺ or Na⁺. According to contact‐angle (CA) analyses, cation treatment did not significantly change the wetting properties of the samples. Batch sorption–desorption experiments showed no clear salt‐treatment effects on the sorption and desorption equilibria or kinetics of NP and Phe. Instead, the sorption coefficients and sorption hysteresis of NP and Phe increased in dry soil. With increasing drying temperature the CA of the soils and the sorption of both xenobiotics increased significantly. We conclude that structural modifications of SOM due to incorporation of polyvalent cations into the interphase structure do not modify the sorption characteristics of the soil for hydrophobic compounds. Instead, increasing hydrophobization of organic soil constituents due to heat treatment significantly increased the accessible sorption sites for nonpolar organic compounds in this soil.     

Cold and hot water–extractable organic matter as indicators of litter decomposition in forest soils

Mild extractions were used as indicators of easily decomposable organic matter (OM). However, the chemical composition of extracted OM often remained unclear. Therefore, the composition of cold and hot water–extractable OM was investigated in the O horizons (Oi, Oe, Oa) of a 170 y old beech stand (Fagus sylvatica) in the Ore Mtns., SE Germany. To simulate litter decomposition, the O horizon samples were incubated for 1 week under defined conditions. Cold‐ and hot‐water extracts were analyzed and chemically characterized by pyrolysis–field ionization mass spectrometry (Py‐FIMS). The C and N concentrations were always lower in the cold‐(C: 2.69 to 3.95 g kg^–1; N: 0.14 to 0.29 g kg^–1) than in the hot‐water extracts (C: 13.77 to 15.51 g kg^–1; N: 0.34 to 0.83 g kg^–1). The C : N ratios of both extracts increased with increasing depth. Incubation increased the concentrations of C and N in all water extracts, while C : N ratios of extracts decreased. The molecular‐chemical composition of cold and hot water–extracted OM revealed distinct differences. Generally, cold water–extracted OM was thermally more stable than hot water–extracted OM. The mass spectra of the hot water–extracted organic matter revealed more intensive signals of carbohydrates, phenols, and lignin monomers. Additionally, the n‐C₂₈ fatty acid and the n‐C₃₈–to–n‐C₅₂ alkyl monoesters clearly distinguished the hot‐ from the cold‐water extract. A principle‐component analysis visualized (1) alterations in the molecular‐chemical composition of cold‐ and hot‐water extracts due to previous incubation of the solid O horizon samples and (2) a decomposition from the Oi to the Oh horizon. This provides evidence that the macromorphological litter decomposition was reflected by the chemical composition of water extracts, and that Py‐FIMS is well‐suited to explain at the molecular level why OM decomposability is correlated with water‐extracted C.     

Labile organic matter fractions as early‐season nitrogen supply indicators in manure‐amended soils

Soil test indicators are needed to predict the contribution of soil organic N to crop N requirements. Labile organic matter (OM) fractions containing C and N are readily metabolized by soil microorganisms, which leads to N mineralization and contributes to the soil N supply to crops. The objective of this study was to identify labile OM fractions that could be indicators of the soil N supply by evaluating the relationship between the soil N supply, the C and N concentrations, and C/N ratios of water extractable OM, hot‐water extractable OM, particulate OM, microbial biomass, and salt extractable OM. Labile OM fractions were measured before planting spring wheat (Triticum aestivum L.) in fertilized soils and the soil N supply was determined from the wheat N uptake and soil mineral N concentration after 6 weeks. Prior to the study, fertilized sandy loam and silty clay soils received three annual applications of 90 kg available N (ha · y)^?1 from mineral fertilizer, liquid dairy cattle manure, liquid swine manure or solid poultry litter, and there was a zero‐N control. Water extractable organic N was the only labile OM fraction to be affected by fertilization in both soil types (P < 0.01). Across both test soils, the soil N supply was significantly correlated with the particulate OM N (r = 0.87, P < 0.001), the particulate OM C (r = 0.83, P < 0.001), and hot‐water extractable organic N (r = 0.81, P < 0.001). We conclude that pre‐planting concentrations of particulate OM and hot‐water extractable organic N could be early season indicators of the soil N supply in fertilized soils of the Saint Lawrence River Lowlands in Quebec, Canada. The suitability of these pre‐planting indicators to predict the soil N supply under field conditions and in fertilized soils from other regions remains to be determined.     

Effects of land use and mineral characteristics on the organic carbon content,and the amount and composition of Na‐pyrophosphate‐soluble organic matter,in subsurface soils

Land use and mineral characteristics affect the ability of surface as well as subsurface soils to sequester organic carbon and their contribution to mitigation of the greenhouse effect. There is less information about the effects of land use and soil properties on the amount and composition of organic matter (OM) for subsurface soils as compared with surface soils. Here we aimed to analyse the long‐term (≥ 100 years) impact of arable and forest land use and soil mineral characteristics on subsurface soil organic carbon (SOC) contents, as well as on amount and composition of OM sequentially separated by Na pyrophosphate solution (OM(PY)) from subsurface soil samples. Seven soils with different mineral characteristics (Albic and Haplic Luvisol, Colluvic and Haplic Regosol, Haplic and Vertic Cambisol, Haplic Stagnosol) were selected from within Germany. Soil samples were taken from subsurface horizons of forest and adjacent arable sites continuously used for >100 years. The OM(PY) fractions were analysed for their OC content (OC_PY) and characterized by Fourier transform infrared spectroscopy. Multiple regression analyses for the arable subsurface soils indicated significant positive relationships between the SOC contents and combined effects of the (i) exchangeable Ca (Ca_ex) and oxalate‐soluble Fe (Fe_ox) and (ii) the Ca_ex and Al_ox contents. For these soils the increase in OC (OC_PY multiplied by the relative C=O content of OM(PY)) and increasing contents of Ca_ex indicated that OM(PY) mainly interacts with Ca²⁺. For the forest subsurface soils (pH < 5), the OC_PY contents were related to the contents of Na‐pyrophosphate‐soluble Fe and Al. The long‐term arable and forest land use seems to result in different OM(PY)‐mineral interactions in subsurface soils. On the basis of this, we hypothesize that a long‐term land‐use change from arable to forest may lead to a shift from mainly OM(PY)‐Ca²⁺ to mainly OM(PY)‐Fe³⁺ and ‐Al³⁺ interactions if the pH of subsurface soils significantly decreases to <5.     

Interpretation of infrared spectra for OM characterization of soil structural surfaces of Bt‐horizons

The surfaces of macropores or aggregates can act as hot spots for biogeochemical processes and solute transport during preferential flow. For the characterization of organic matter (OM) at macropore surfaces non‐destructive methods have been applied such as diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). However, effects of organic components on DRIFT signal intensities are often difficult to distinguish from those of mineral components. Here, DRIFT spectra from intact earthworm burrow walls and coated cracks were re‐evaluated to improve the interpretation of C–H and C=O bands. We compared DRIFT and transmission Fourier transform infrared (FTIR) spectra of entire samples that were from the same pedogenetic soil horizon (Bt) but different in mineral composition and texture (i.e., glacial till vs. loess). Spectra of incinerated samples were subtracted from the original spectra. Transmission FTIR and DRIFT spectra were almost identical for entire soil samples. However, the DRIFT spectra were affected by the bulk mode bands (i.e., wavenumbers 2000 to 1700 cm^?1). These bands affected spectral resolution and reproducibility. The ratios between C–H and C=O band intensities as indicator for OM quality obtained with DRIFT were smaller than those obtained from transmission FTIR. The results demonstrated that DRIFT and transmission FTIR data required separate interpretations. DRIFT spectroscopy as a non‐destructive method for analyzing OM composition at intact surfaces in structured soils could be calibrated with information obtained with the more detailed transmission FTIR and complementary methods. Spectral subtraction procedure was found useful to reduce effects of mineral absorption bands. The improved DRIFT data may be related to other soil properties (e.g., cation exchange capacity) of hot spots in structured soils.     

Spectroscopic characterization of mucilage (Chia seed) and polygalacturonic acid

Polygalacturonic acid (PGA) has frequently been suggested and used as a model substance for studying mucilage properties and effects in soil. While PGA has a defined chemical structure, the composition of mucilage as natural product can vary in space and time depending on the plant and soil conditions. However, it is still unclear if PGA can be used as surrogate for original mucilage when considering soil–mucilage interactions in the rhizosphere. Here the organic matter (OM) composition of PGA was compared with that of Chia seed mucilage and small‐scale spatial distribution of OM composition in mucilage droplets was analysed using Fourier transform mid infrared spectroscopy in KBr‐transmission technique (FTIR). Selected regions of dried Chia seed mucilage droplets were analysed using micro‐ Fourier transform mid infrared spectroscopy in transflection technique (micro‐FTIR). For PGA, the FTIR spectra revealed lower C–H/C=O and higher C=O/C–O–C ratios as compared to Chia seed mucilage, indicating a relatively lower potential hydrophobicity and higher sorption capacity of the OM in PGA than OM in mucilage. The micro‐FTIR spectra revealed that the potential hydrophobicity of a single freeze‐dried mucilage droplet was higher at the tip as compared to regions located above the tip. The results suggest that the use of PGA as model substance for mucilage is limited especially when trying to imitate the sorption and wettability properties of the Chia seed mucilage OM. The spatial heterogeneity in OM composition as well as shifts in maxima of C=O and O–H bands in micro FTIR spectra of the cross sectioned mucilage droplet suggest that the composition of mucilage is changing with time. These findings may help initiating future studies on the dynamics and variability of OM composition of mucilage.     

Cation binding in a soil with low exchange capacity: Implication for the structural rigidity of soil organic matter

Two previous studies suggested that part of the cation sorption sites in soil organic matter with low exchange capacity have to be considered as “lonely”, i.e., too far from each other to allow direct cross‐linking by bivalent cations. The objective of this contribution was to understand the mechanisms controlling structural rigidity and physicochemical aging of the SOM (soil organic matter) and the role of water molecule bridges (WaMB) therein. For this, we evaluated the matrix rigidity of an organic surface layer of a Haplic Podzol on a quantitative basis, by assessing WaMB transition temperature (T*) directly after treatment with bivalent cations (Mg²⁺, Ca²⁺, or Ba²⁺) and after eight weeks of aging. Cation loading as well as cation type influenced matrix rigidity. Ba²⁺ induced the most rigid matrix and Mg²⁺ the weakest, which is in line with their binding strength in terms of Langmuir coefficient. The matrix rigidity increased with the cross‐linking activity, which is the product of loading and Langmuir constant of the respective cation. The aging process, however, was slowed down by the initial matrix rigidity, and the rigidity of the aged matrix decreased with increasing Langmuir constant. The degree of aging increased with increasing hydration enthalpy of the cation and decreased with increasing cation loading. Thus, directly after cation treatment, direct cross‐links by multivalent cations were most relevant, but WaMB increasingly gained influence on the matrix rigidity during aging. The untreated sample revealed a considerable number of WaMB, resulting in a fairly rigid and strongly cross‐linked matrix which, however, flexibly reacts on external influences like change in cation concentration or relative humidity. With these findings, the ideas on the relevance of indirect CaB‐WaMB associations between distant sorption sites for the rigidity and flexibility of the OM matrix as proposed in previous studies were confirmed on a mechanistic basis in this study.     

Soil organic matter characterization of temperate peatland soil with FTIR‐spectroscopy: effects of mire type and drainage intensity

Peatlands are an important component of the global carbon cycle because they comprise huge amounts of terrestrial carbon (C). Different conditions during peat formation and secondary peat decomposition affect the quantity and composition of soil organic matter (SOM) in peats. There are few comparative studies on the chemical composition of SOM in temperate peatland soil. This study investigates compositional changes of SOM functional groups in peats and corresponding peat‐forming plants by Fourier transform infrared (FTIR) spectroscopy. Three plant samples and 29 peat samples were taken from seven temperate peatland sites with different genesis and land‐use intensity. Site‐specific differences, such as genesis of the peat, were found to be reflected in the FTIR spectra. In general, there was more variation in FTIR spectra in samples from fens than in those from bogs and peat‐forming plants. The samples from fens have a smaller C–H absorption band than those from bogs and plants, which reflects greater biochemical activity in the minerotrophic than ombrotrophic environments. In addition to peat genesis, drainage and secondary peat decomposition also affect SOM composition substantially. The larger amounts of aliphatic compounds in undrained peats could be explained by selective preservation caused by anaerobic conditions. With increasing drainage of the sites, there was a decrease in the C–H absorption that was accompanied by a relative increase in C=O absorption. These changes in absorption intensities reflect the enhanced aerobic decomposition and mineralization that accompanies drainage and land‐use intensity. However, the ‘degree of peat decomposition’, a diagnostic tool used in the field, is not reflected by OM composition determined by FTIR spectroscopy. Our results contribute to further understanding of changes in SOM composition during peat formation and processes of secondary decomposition caused by drainage.     

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

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

Glomalin amount and compositional variation,and their associations with soil properties in farmland,northeastern China

Glomalin‐related soil protein (GRSP) is well‐known for its soil conditioning functions, but compositional traits are rarely considered. Farmland in northeastern China is the most important commercial grain basis, and soil degradation becomes the bottleneck for keeping crop productivity. The objective of this study was to uncover the possible associations between GRSP (amount and composition) and soil properties, and make suggestions for soil improvement from soil glomalin rehabilitation in northeastern China. Here, spatial variation in GRSP amount (Easily‐extractable‐GRSP, EE‐GRSP; Total‐GRSP, T‐GRSP) and its compositional traits from infrared spectroscopy, UV‐absorbance, X‐ray diffraction (XRD) and 3‐D fluorescence spectroscopy were surveyed in 360 soil samples across northeastern China, and their association with 11 soil properties were also analyzed for finding the possible influence of soil properties on GRSP composition in farmland. There about 3‐fold spatial variation in GRSP amount was observed, while functional group variations were ranged from 1.2‐fold (O–H & N–H stretching) to 2.4‐fold (C–O stretching & O–H bending of –COOH) in different locations. The XRD showed that grain size was 113–180Å and crystallinity was 0.71–1.42%, and GRSP contained seven fluorescent compounds of tyrosine‐like, tryptophan‐like, fulvic acid‐like, soluble microbial byproduct, humic acid‐like, nitrobenzoxadidole‐like, and calcofluor white‐like. Both, EE‐GRSP and T‐GRSP positively associated with soil organic carbon (SOC), soil N (SON), soil P (SOP), alkali‐hydrolyzed N (AN), available P (AP), available K (AK), and soil water, while negatively associated with soil pH and soil bulk density. Structural equation model (SEM) analysis indicates that direct effects on GRSP amounts were mainly from soil bulk density (coefficient: –0.27), soil pH (coefficients: –0.51 to –0.57), SOC (coefficients: 0.51 to 0.69) and AP (coefficients: 0.18 to 0.26), while all other soil properties had indirect effects on GRSP amounts via their close associations with these four parameters. Compared with the GRSP amounts, soil properties laid fewer effects on GRSP compositional traits. Of 16 compositional traits, five of them showed possible regulations from soil properties, which were three infrared functional groups (IR‐II: aliphatic C–H stretching; IR‐V: C–O stretching & O–H bending of –COOH; IR‐VII: O–H binding) and two fluorescent compounds (tyrosine‐like and humic acid‐like). SEM analysis indicates that soil water, pH and EC could directly affect IR‐II, IRV, tyrosine‐like and humic acid‐like, while available nutrients showed more evident influences on infra‐red functional groups than total amounts of N, P and K. Moreover, SOC, as a media of various soil nutrients, gave the strongest influence on GRSP compositional traits. As a supplement to previous studies, we found that GRSP is a mixture of different fluorescent compounds with different functional groups. Our findings highlight that soil properties could strongly change both GRSP accumulation in soil and their compositional traits, and the definition of the most probable soil properties in regulating glomalin amount and composition in this paper could favor good soil management in farmland at northeastern China.     

Interactions between cations and water molecule bridges in soil organic matter

Purpose

Nutrient release, soil wettability, water binding, and matrix rigidity of soil organic matter (SOM) can be affected by cross-links between segments of SOM, cations, and water molecule bridges (WaMB). Not all cation effects on SOM can be explained with the currently accepted idea that multivalent cations cross-link organic matter segments via direct cation bridges (CaB). The objective was to understand these interactions and their effect on SOM matrix rigidity and wettability.

Materials and methods

We modified cation composition of two peats and an organic surface layer (OSL) using cation exchange resin to remove cations and solutions of Na⁺, Ca²⁺, or Al³⁺ to enrich samples with cations. SOM matrix rigidity was determined at 4 and >8 weeks after treatment via the WaMB transition temperature T*, using differential scanning calorimetry. Wettability was measured via sessile drop contact angle (CA).

Results and discussion

The effect of cation removal on T* depended on cation exchange capacity and initial cation content. Cation addition to OSL increased T*. This effect increased with increasing cation loading and valency, and T* correlated with CA. Classical cross-linking can neither explain the higher heterogeneous matrix of Ca-treated than Al-treated samples nor the aging-induced convergence of T* for different cations and concentrations. The latter is likely due to interaction between CaB and WaMB in SOM.

Conclusions

Associations of CaB and WaMB evolve slowly and form a supramolecular network in SOM. Those dynamic associations can fix molecular arrangements inducing water repellency and increase kinetic barriers for the release and uptake of water and nutrients from aged soil.     

Soil organic matter fractionation as a tool for predicting nitrogen mineralization in silty arable soils

After decades of searching for a practical method to estimate the N mineralization capacity of soil, there is still no consistent methodology. Indeed it is important to have practical methods to estimate soil nitrogen release for plant uptake and that should be appropriate, less time consuming, and cost effective for farmers. We fractionated soil organic matter (SOM) to assess different fractions of SOM as predictors for net N mineralization measured from repacked (disturbed) and intact (undisturbed) soil cores in 14 weeks of laboratory incubations. A soil set consisting of surface soil from 18 cereal and root‐cropped arable fields was physically fractionated into coarse and fine free particulate OM (coarse fPOM and fine fPOM), intra‐microaggregate particulate OM (iPOM) and silt and clay sized OM. The silt and clay sized OM was further chemically fractionated by oxidation with 6% NaOCl to isolate an oxidation‐resistant OM fraction, followed by extraction of mineral bound OM with 10% HF (HF‐res OM). Stepwise multiple linear regression yielded a significant relationship between the annual N mineralization (kg N/ha) from undisturbed soil and coarse fPOM N (kg N/ha), silt and clay N (kg N/ha) and its C:N ratio (R² = 0.80; P < 0.01). The relative annual N mineralization (% of soil N) from disturbed soils was related to coarse fPOM N, HF‐res OC (% of soil organic carbon) and its C:N ratio (R² = 0.83; P < 0.01). Physical fractions of SOM were thus found to be the most useful predictors for estimating the annual N mineralization rate of undisturbed soils. However, the bioavailability of physical fractions was changed due to the disturbance of soil. For disturbed soils, a presumed stable chemical SOM fraction was found to be a relevant predictor indicating that this fraction still contains bio‐available N. The latter prompted a revision in our reasoning behind selective oxidation and extraction as tools for characterizing soil organic N quality with respect to N availability. Nonetheless, the present study also underscores the potential of a combined physical and chemical fractionation procedure for isolating and quantifying N fractions which preferentially contribute to bulk soil N mineralization. The N content or C:N ratio of such fractions may be used to predict N mineralization in arable soils.     

The contribution of various organic matter fractions to soil–water interactions and structural stability of an agriculturally cultivated soil

The presence and mutual interactions of soil organic matter (SOM) and clay particles are major factors determining soil structural stability. In the scope of agricultural management and environmental sustainability, it remains unclear how various mineral and organic matter (OM) fractions, OM–clay interactions and swelling processes in the interparticle space determine soil–water interactions and thus soil structural stability. To investigate this issue, we isolated the mineral and OM fractions of an agriculturally cultivated silty loam soil by soil density fractionation and assessed their hydration characteristics and effects on soil structural stability combining ¹H‐NMR relaxometry, soil rheology and single wet‐sieving of soil aggregates. The results showed that agricultural management practices, in particular compost and ploughing, as well as various OM–clay interactions significantly affected soil–water interactions and soil structural stability. On the one hand, ploughing reduced soil structural stability by promoting clay swelling as a result of disrupted soil structures and reduced SOM content. On the other hand, compost treatment and reduced tillage increased soil structural stability. In all cases, soil density fractionation showed that compost‐derived particulate organic matter (POM) and mineral‐associated organic matter (MAOM) restricted clay swelling and resulted in a highly porous and mechanically stable soil matrix. In particular, POM increased soil structural stability by acting as nucleus for soil aggregation and by restricting clay swelling via its presence as solid, granular interparticulate material. In contrast, MAOM seemed to restrict clay swelling via clay surface covering and the formation of viscous interparticulate hydrogel structures.     

Considerations on cross‐linking by bivalent cations in soil organic matter with low exchange capacity

A soil's cation exchange capacity (CEC) is expected to be relatively inert against changes in cation loading. In this study, we treated a soil sample originating from the organic layer of a forest soil with various bivalent cations after removing the native cations. Sorption isotherms and cation exchange capacity were determined, the latter using the BaCl₂ method. Sorption showed Langmuir characteristics, with the maximum coverage (Q_max) increasing in the order Ba²⁺ < Ca²⁺ < Mg²⁺, but being clearly smaller than the initial load of native exchangeable cations. The Langmuir coefficient, k_Me, depended oppositely to the order obtained for Q_max. CEC increased upon cation treatment and it varied by a factor of almost two. The unexpected variation of CEC was explained by the low cation exchange capacity of the organic matter such that not all functional groups are close enough to be bridged and the second charge of a bivalent cation is not neutralized by the organic functional group. The Langmuir sorption type, and Q_max being smaller than the content of sorption sites and being largest for Mg, suggested that only a part of the sites can be cross‐linked and at least part of the cross‐links are formed by hydrated cations. Thermodynamic considerations allowed reconstruction of two contrasting processes during CEC determination by Ba²⁺: Case A: the disruption of cross‐links, which increases with the cationic strength and the cation load before CEC determination, but does not require structural re‐orientation in the SOM matrix, and Case B: the formation of new cross‐links during CEC determination, depending only on the content of unoccupied sites before CEC determination and requiring structural re‐organization of the matrix and thus a minimum matrix flexibility. The use of bivalent cations for CEC determination may thus result in an overestimation of CEC for organic matter with low CEC. This has, however, promising potential when comparing CEC determined with monovalent cations and bivalent cations. Using a set of bivalent cations, may allow probing distribution of distances between functional groups in the organic matter and even characterize the matrix rigidity of the cation‐cross‐linked network.     

Soil organic matter composition and soil lightness

Relationships between soil lightness, soil organic matter (SOM) composition, content of organic C, CaCO₃, and texture were studied using 42 top‐soil horizons from different soil types located in southern Germany. SOM composition was determined by CPMAS ¹³C NMR spectroscopy, soil color was measured by diffuse‐reflectance spectrophotometry and given in the CIE L*a*b* color coordination system (Commission Internationale de l'Eclairage, 1978). Multiple‐regression analysis showed, that soil lightness of top‐soil horizons is principally determined by OC concentration, but CaCO₃ and soil texture are also major variables. Soil lightness decreased with increasing OC content. Carbonate content had an important effect on soil lightness even at low concentrations due to its lightening property. Regressions between soil lightness and organic C content were strongly linear, when the soils were differentiated according to texture and CaCO₃ content. The aryl‐C content was the only SOM component which correlated significantly with soil lightness (r_S = –0.87). In the linear regressions carried out on the different soil groups, soil aryl‐C content was a more significant predictor for soil lightness than total OC content.     

Examination into the Accuracy of Exchangeable Cation Measurement in Saline Soils

Abstract

Despite the increasing prevalence of salinity worldwide, the measurement of exchangeable cation concentrations in saline soils remains problematic. Two soil types (Mollisol and Vertisol) were equilibrated with a range of sodium adsorption ratio (SAR) solutions at various ionic strengths. The concentrations of exchangeable cations were then determined using several different types of methods, and the measured exchangeable cation concentrations were compared to reference values. At low ionic strength (low salinity), the concentration of exchangeable cations can be accurately estimated from the total soil extractable cations. In saline soils, however, the presence of soluble salts in the soil solution precludes the use of this method. Leaching of the soil with a prewash solution (such as alcohol) was found to effectively remove the soluble salts from the soil, thus allowing the accurate measurement of the effective cation exchange capacity (ECEC). However, the dilution associated with this prewashing increased the exchangeable calcium (Ca) concentrations while simultaneously decreasing exchangeable sodium (Na). In contrast, when calculated as the difference between the total extractable cations and the soil solution cations, good correlations were found between the calculated exchangeable cation concentrations and the reference values for both Na (Mollisol: y=0.873x and Vertisol: y=0.960x) and Ca (Mollisol: y=0.901x and Vertisol: y=1.05x). Therefore, for soils with a soil solution ionic strength greater than 50 mM (electrical conductivity of 4 dS/m) (in which exchangeable cation concentrations are overestimated by the assumption they can be estimated as the total extractable cations), concentrations can be calculated as the difference between total extractable cations and soluble cations.     

The effects of compost in a rice–wheat cropping system on aggregate size,carbon and nitrogen content of the size–density fraction and chemical composition of soil organic matter,as shown by 13C CP NMR spectroscopy

We investigated whether the long‐term application of compost from agricultural waste improved soil physical structure, fertility and soil organic matter (SOM) storage. In 2006, we began a long‐term field experiment based on a rice–wheat rotation cropping system, having a control without fertilizer (NF) and three treatments: chemical fertilizers (CF), pig manure compost (PMC) and a prilled mixture of PMC and inorganic fertilizers (OICF). Following the harvest of wheat in 2010, the mean‐weight diameter (MWD) of water‐stable aggregates and the concentration of C and N in bulk soil (0–20 cm; <2 mm fraction) were significantly greater (P < 0.05) in PMC and NF plots than in CF or OICF plots. Pig manure compost significantly increased the proportion of >5‐mm aggregates, whereas CF significantly increased the proportion of 0.45‐ to 1‐mm aggregates. The C and N contents of all density fractions were greater in PMC than in other treatments with levels decreasing in the following order: free particulate organic matter (fPOM) >occluded particulate organic matter (oPOM) > mineral‐combined SOM (mineral–SOM). Solid‐state ¹³C CPMAS NMR spectra showed that alkyl C/O‐alkyl C ratios and aromatic component levels of SOM were smaller in PMC and OICF plots than in CF plots, suggesting that SOM in PMC and OICF plots was less degraded than that in CF plots. Nevertheless, yields of wheat in PMC and NF plots were smaller than those in CF and OICF plots, indicating that conditions for producing large grain yields did not maintain soil fertility.