Explaining soil organic matter composition based on associations between OM and polyvalent cations

Site conditions and soil management determine the content and the composition of soil organic matter (SOM). Organic matter (OM) is characterized by functional groups, which preferentially interact with polyvalent cations and soil minerals. These interactions could perhaps explain the site‐specific composition of bulk SOM and a pyrophosphate‐soluble OM fraction (OM‐PY) using basic soil properties. The objective of this study was to test a simplified model for the interactions between OM and polyvalent cations (i.e., Ca, Mg, Al, Fe, and Mn) by using data from soils from long‐term field experiments. The model considered (1) OM–cation, (2) OM–cation‐mineral, and (3) OM–mineral associations and assumed that the availability of the cation's coordination sites for the interaction with OM depends on these three types of associations. The test was carried out using data (topsoil) from differently fertilized plots from three long‐term field experiments (Halle, Bad Lauchstädt, Rotthalmünster). The composition of SOM and OM‐PY was characterized by the relationship of the ratio of the C=O (i.e., here indicating both carbonylic and carboxylic groups) versus C–O–C absorption band intensities obtained from the Fourier transform infrared (FTIR) spectra with the content of exchangeable, oxalate‐, and dithionite‐extractable polyvalent cations. The assumed associations between the OM and cations and the availability of the coordination sites explained most of the variations in the C=O/C–O–C ratios of the SOM, and fewer variations in the OM‐PY, when using the site‐specific exchangeable and oxalate‐extractable cation contents. The C=O/C–O–C ratios of the OM‐PY were site‐independent for samples from plots that regularly received farmyard manure. The results suggested that a simplified model that considers the polyvalent cation content weighted by the number of coordination sites per cation according to the type of association could be used to improve the explanation of site‐specific differences in the OM composition of arable soils.     

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.     

Gel formation mechanism and gel properties controlled by Ca2+ in chia seed mucilage and model substances

Polygalacturonic acid (PGA) is considered as a model substance for mucilage to study mucilage–soil interactions, assuming that the gel formation mechanism of mucilage is comparable to the one of PGA. However, some studies question the accepted hypothesis, which states that, like for PGA, this mechanism relies on cross‐links between uronic acid and calcium for mucilage. The aim of this study was therefore to understand the influence of the abundance and degree of esterification of uronic acids and the influence of calcium on the gel formation mechanism in mucilage as compared to model substances. The mucilage used was from chia seeds, as it is easily available in great quantity and has gel properties shared by root mucilage. Results reported here demonstrate that, while the gel formation mechanism of PGA relied on specific cross‐links with calcium and led to heterogeneous gels, low‐methoxy pectin (LMP) formed homogeneous calcium gels also characterized by nonspecific ionic interactions with calcium. On the contrary, despite similar uronic acid content to LMP, chia seed mucilage was mostly governed by weak electrostatic interactions between entangled polymer chains, which conferred the gel poor water retention. Addition of calcium reduced repulsion and molecular expansion, resulting in a reduction of the water content in chia seed mucilage. Finally, the discrepancies between PGA, LMP and chia seed mucilage discredit the use of PGA as model for chia seed mucilage. Comparison with root mucilage is still needed. This study offers the keys for further mechanistic understanding on the influence of mucilage on soil properties.     

Physical carbon‐sequestration mechanisms under special consideration of soil wettability

The protective impact of aggregation on microbial degradation through separation has been described frequently, especially for biotically formed aggregates. However, to date little information exists on the effects of organic‐matter (OM) quantity and OM quality on physical protection, i.e., reduced degradability by microorganisms caused by physical factors. In the present paper, we hypothesize that soil wettability, which is significantly influenced by OM, may act as a key factor for OM stabilization as it controls the microbial accessibility for water, nutrients, and oxygen in three‐phase systems like soil. Based on this hypothesis, the first objective is to evaluate new findings on the organization of organo‐mineral complexes at the nanoscale as one of the processes creating water‐repellent coatings on mineral surfaces. The second objective is to quantify the degree of alteration of coated surfaces with regard to water repellence. We introduce a recently developed trial that combines FTIR spectra with contact‐angle data as the link between chemical composition of OM and the physical wetting behavior of soil particles. In addition to characterizing the wetting properties of OM coatings, we discuss the implications of water‐repellent surfaces for different physical protection mechanisms of OM. For typical minerals, the OM loading on mineral surfaces is patchy, whereas OM forms nanoscaled micro‐aggregates together with metal oxides and hydroxides and with layered clay minerals. Such small aggregates may efficiently stabilize OM against microbial decomposition. However, despite the patchy structure of OM coating, we observed a relation between the chemical composition of OM and wettability. A higher hydrophobicity of the OM appears to stabilize the organic C in soil, either caused by a specific reduced biodegradability of OM or indirectly caused by increased aggregate stability. In partly saturated nonaggregated soil, the specific distribution of the pore water appears to further affect the mineralization of OM as a function of wettability. We conclude that the wettability of OM, quantified by the contact angle, links the chemical structure of OM with a bundle of physical soil properties and that reduced wettability results in the stabilization of OM in soils.     

Millimetre‐scale distribution of organic matter composition at intact biopore and crack surfaces

Structured subsoil horizons are characterized by biopores and shrinkage cracks, which may serve as preferential flow paths. The surfaces of cracks and biopores may be coated by clay‐organic material. The spatially‐distributed organic matter (OM) composition at such structural surfaces was studied at the millimetre scale using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy in the mid‐infrared range (MIR). Intact biopores such as earthworm burrows and root channels, and crack surfaces of nine subsoil horizons were analysed. The samples were from arable and forest Luvisols, one Regosol, one Stagnosol and Cambisols developed from loess, till, mudstone and limestone. For better comparison between soils, the DRIFT signal intensities were corrected for the particle‐size effects. The OM was characterized by the ratio between alkyl‐ (C–H) and carbonyl (C=O) functional groups (C–H/C=O), which represent an index of the potential wettability (PWI) of the OM. The PWI was larger for biopores than for crack surfaces and the soil matrix, indicating a smaller potential wettability of OM at biopore surfaces. The millimetre‐scale spatial variability of OM was especially large for the surfaces of root channels. Samples from till‐derived Luvisols had smaller PWI (with greater potential wettability than surfaces from loess‐derived Luvisols) than other soil types. The mean PWI of the arable Luvisol crack surfaces was less than that of the forest Luvisol samples. The results suggest that the spatial distribution of OM properties at intact structural surfaces may be important for describing sorption and mass transfer processes during preferential flow.     

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 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.     

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.     

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.     

Precipitation of enzymes and organic matter by aluminum—Impacts on carbon mineralization

The precipitation of dissolved organic matter (DOM) by aluminum (Al) results in a stable soil organic matter (OM) fraction. Extracellular enzymes can also be removed from soil solution by sorption or precipitation, but whether this affects their activity and their importance for carbon (C) mineralization is largely unknown. We studied the activity of eight extracellular enzymes, precipitated by Al together with DOM, in relation to C mineralization of the precipitated OM. Dissolved OM was obtained from the Oi and Oa horizon of two forest soils and precipitated at different Al : C ratios and pH values to achieve a large variation in composition and C mineralization of precipitated OM. All eight enzymes were present in a functional state in precipitated OM. On average 53% of DOM was precipitated, containing on average 17%–41% of the enzyme activity (EA) involved in C degradation (chitinase, cellobiohydrolase, β‐glucosidase, glucuronidase, lacasse, and xylosidase) previously present in soil solution. In contrast, on average only 4%–7% of leucine‐aminopeptidase and acid‐phosphatase activity was found in precipitated OM. The EA found in precipitates significantly increased the percentage of C mineralized of precipitated OM, with a stronger influence of C‐degrading enzymes than enzymes involved in N and P cycling. However, after 8 weeks of incubation the correlations between EA and C mineralization disappeared, despite substantial EA being still present and only 0.5%–7.7% of C mineralized. Thus, degradation of precipitated OM seems to be governed by EA during the first degradation phase, but the long‐term stability of precipitated OM is probably related to its chemical properties.     

The phenanthrene‐sorptive interface of an arable topsoil and its particle size fractions

Sorption of organic chemicals in soil is affected by the properties and availability of surfaces. These surfaces are composed of diverse mineral, organic and biological components, forming a soil's ‘biogeochemical interface’. Phenanthrene was used to probe the hydrophobic sorptive capacity of the interface of an arable soil. Batch sorption experiments were carried out with the bulk soil as well as the fine (0.2–6.3 µm) and coarse (6.3–63 µm) particle size fractions of two arable topsoil samples with different organic matter (OM) contents from a Eutric Cambisol. The specific surface area (SSA) of the bulk soil and particle size fractions was determined by BET‐N₂ and EGME sorption. OM composition was characterized by solid‐state ¹³C NMR spectroscopy. No clear relationship was found between phenanthrene sorption and SSA. We conclude that phenanthrene probes a specific fraction of the soil interface that is not well represented by the traditional methods of SSA detection such as BET‐N₂ and EGME sorption. The sorption behaviour of phenanthrene may therefore provide a useful additional tool to characterize the specific affinity of the soil biogeochemical interface for hydrophobic molecules. Sorption capacity for phenanthrene increased after particle‐size fractionation, indicating that the reduced availability of the interface caused by the aggregated structure is important for the sorptive capacity of a soil. This should be considered when projecting data obtained from extensively treated and fractionated samples to the actual interaction with biogeochemical interfaces as they are present in soil.     

Long‐term fertilization and manuring effects on physically separated soil organic‐matter pools under continuous wheat cropping at a rainfed semiarid site in China

An essential prerequisite for a sustainable soil use is to maintain a satisfactory soil organic‐matter (OM) level. This might be achieved by sound fertilization management, though impacts of fertilization on OM have been rarely investigated with the aid of physical fractionation techniques in semiarid regions. This study aimed at examining changes in organic C (OC) and N concentrations of physically separated soil OM pools after 26 y of fertilization at a site of the semiarid Loess Plateau in China. To separate sensitive OM pools, total macro‐OM (> 0.05 mm) was obtained from bulk soil by wet‐sieving and then separated into light macro‐OM (< 1.8 g cm^–3) and heavy macro‐OM (> 1.8 g cm^–3) subfractions; bulk soil was also differentiated into light OM (< 1.8 g cm^–3) and mineral‐associated OM (> 1.8 g cm^–3). Farmyard manure increased concentrations of total macro‐OC and N by 19% and 25%, and those of light fraction OC and N by 36% and 46%, compared to no manuring; both light OC and N concentrations but only total macro‐OC concentration responded positively to mineral fertilizations compared to no mineral fertilization. This demonstrated that the light‐fraction OM was more sensitive to organic or inorganic fertilization than the total macro‐OM. Mineral‐associated OC and N concentrations also increased by manuring or mineral fertilizations, indicating an increase of stable OM relative to no fertilization treatment, however, their shares on bulk soil OC and N decreased. Mineral fertilizations improved soil OM quality by decreasing C : N ratio in the light OM fraction whereas manuring led to a decline of the C : N ratio in the total macro‐OM fraction, with respect to nil treatment. Further fractionation of the total macro‐OM according to density clarified that across treatments about 3/4 of total macro‐OM was associated with minerals. Thus, by simultaneously applying particle‐size and density separation procedures, we clearly demonstrated that the macro‐OM differed from the light OM fraction not only in its chemical composition but also in associations with minerals. The proportion of the 0.5–0.25 mm water‐stable aggregates of soil was higher under organic or inorganic fertilizations than under no manure or no mineral fertilization, and increases in OC and N concentrations of water‐stable aggregates as affected by fertilization were greater for 1–0.5 and 0.5–0.25 mm classes than for the other classes. Results indicate that OM stocks in different soil pools can be increased and the loose aggregation of these strongly eroded loess soils can be improved by organic or inorganic fertilization.     

Use of mid‐infrared spectroscopy in the diffuse‐reflectance mode for the prediction of the composition of organic matter in soil and litter

Mid‐infrared spectroscopy (MIRS) is assumed to be superior to near‐infrared spectroscopy (NIRS) for the prediction of soil constituents, but its usefulness is still not sufficiently explored. The objective of this study was to evaluate the ability of MIRS to predict the chemical and biological properties of organic matter in soils and litter. Reflectance spectra of the mid‐infrared region including part of the near‐infrared region (7000–400 cm^–1) were recorded for 56 soil and litter samples from agricultural and forest sites. Spectra were used to predict general and biological characteristics of the samples as well as the C composition which was measured by ¹³C CPMAS‐NMR spectroscopy. A partial least‐square method and cross‐validation were used to develop equations for the different constituents over selected spectra ranges after several mathematical treatments of the spectra. Mid‐infrared spectroscopy predicted well the C : N ratio: the modeling efficiency EF was 0.95, the regression coefficient (a) of a linear regression (measured against predicted values) was 1.0, and the correlation coefficient (r) was 0.98. Satisfactorily (EF ≥ 0.70, 0.8 ≤ a ≤ 1.2, r ≥ 0.80) assessed were the contents of C, N, and lignin, the production of dissolved organic carbon, and the contents of carbonyl C, aromatic C, O‐alkyl C, and alkyl C. However, the N mineralization rate, the microbial biomass and the alkyl–to–aromatic C ratio were predicted less satisfactorily (EF < 0.70). Limiting the sample set to mineral soils did generally not result in improved predictions. The good and satisfactory predictions reported above indicate a marked usefulness of MIRS in the assessment of chemical characteristics of soils and litter, but the accuracies of the MIRS predictions in the diffuse‐reflectance mode were generally not superior to those of NIRS.     

Droplet infiltration and organic matter composition of intact crack and biopore surfaces from clay‐illuvial horizons

The organic matter (OM) in biopore walls and aggregate coatings may be important for sorption of reactive solutes and water as well as for solute mass exchange between the soil matrix and the preferential flow (PF) domains in structured soil. Structural surfaces are coated by illuvial clay‐organic material and by OM of different origin, e.g., earthworm casts and root residues. The objectives were to verify the effect of OM on wettability and infiltration of intact structural surfaces in clay‐illuvial horizons (Bt) of Luvisols and to investigate the relevance of the mm‐scale distribution of OM composition on the water and solute transfer. Intact aggregate surfaces and biopore walls were prepared from Bt horizons of Luvisols developed from Loess and glacial till. The mm‐scale spatial distribution of OM composition was scanned using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The ratio between alkyl and carboxyl functional groups in OM was used as potential wettability index (PWI) of the OM. The infiltration dynamics of water and ethanol droplets were determined measuring contact angles (CA) and water drop penetration times (WDPT). At intact surfaces of earthworm burrows and coated cracks of the Loess‐Bt, the potential wettability of the OM was significantly reduced compared to the uncoated matrix. These data corresponded to increased WDPT, indicating a mm‐scaled sub‐critical water repellency. The relation was highly linear for earthworm burrows and crack coatings from the Loess‐Bt with WDPT > 2.5 s. Other surfaces of the Loess‐Bt and most surfaces of the till‐derived Bt were not found to be repellent. At these surfaces, no relations between the potential wettability of the OM and the actual wettability of the surface were found. The results suggest that water absorption at intact surface structures, i.e., mass exchange between PF paths and soil matrix, can be locally affected by a mm‐scale OM distribution if OM is of increased content and is enriched in alkyl functional groups. For such surfaces, the relation between potential and actual wettability provides the possibility to evaluate the mm‐scale spatial distribution of wettability and sorption and mass exchange from DRIFT spectroscopic scanning.     

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

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

Sorption of iron‐cyanide complexes on goethite investigated in long‐term experiments

The iron‐cyanide complexes ferrocyanide, [Fe^II(CN)₆]^4–, and ferricyanide, [Fe^III(CN)₆]^3–, are anthropogenic contaminants in soil. We investigated their sorption on goethite, α‐FeOOH, in batch experiments in a time range from 1 d to 1 yr, their desorption by phosphate and chloride as well as their surface complexes on goethite by Fourier‐transform infrared spectroscopy (FTIR). The sorption of both complexes continued over the whole time range. Percent desorption of ferricyanide by phosphate decreased, whereas that of ferrocyanide increased until it amounted to approximately 87% for both complexes. By FTIR spectroscopy inner‐sphere complexation of both complexes on the goethite surface was indicated. With both complexes, a Berlin‐Blue‐like layer (Fe₄[Fe(CN)₆]₃) was formed initially on the goethite surface which disappeared with increasing reaction time. After at least 30 d reaction time, ferricyanide was the only sorbed iron‐cyanide complex detected even when ferrocyanide was initially added. This resulted from slow oxidation of ferrocyanide, most probably by dissolved oxygen. Based on all results, we propose that ferricyanide forms monodentate inner‐sphere complexes on the goethite surface.     

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.     

Transitions of water‐drop impact behaviour on hydrophobic and hydrophilic particles

Extreme soil water repellency can have substantial implications for soil hydrology, plant growth and erosion, including enhanced splash erosion caused by raindrop impact. Previous studies of water droplet impact behaviour on man‐made super‐hydrophobic surfaces, with which water‐repellent soil shares similar characteristics, revealed three distinct modes of splash behaviour (rebound, pinning and fragmentation) distinguished by two transition velocities: rebound‐to‐pinning (v_min) and pinning‐to‐fragmentation (v*). By using high‐speed videography of single water droplet impacts we show that splash behaviour is influenced by the hydrophobicity of immobile particles, with hydrophobic glass spheres exhibiting all three modes of splash behaviour in the hydrophobic state but hydrophilic spheres exhibiting solely pinning behaviour. We found that increasing the particle size of fixed glass spheres increases v_min. A study of droplet impact on hydrophobic sand shows that the increased roughness of the immobile particles makes impacting droplets more likely to fragment at slower impact velocities. The mobility of the particles influenced droplet impact behaviour, with loose, hydrophobic particles displaying significantly greater v_min values than their fixed analogues. The surface tension of the water droplet also lifted loose, hydrophobic particles from the surface, forming highly mobile ‘liquid marbles'. Water‐repellent soil was also shown to form ‘liquid marbles' at both the slow (approximately 0.3–2.1 m s^?1) and fast (about 7 m s^?1) droplet impact velocities studied. The observation of very mobile liquid marbles upon water droplet impact on water‐repellent soil is significant as this provided a mechanism that may enhance erosion rates of water‐repellent soil.     

Effect of soil drying on mucilage exudation and its water repellency: a new method to collect mucilage

Despite the importance of mucilage for soil–plant relations, little is known about the effect of soil drying on mucilage exudation. We introduce a method to collect mucilage from maize growing in wet and dry soils. Mucilage was collected from brace roots. The amount of mucilage exuded did not change with soil water content and transpiration rate. Mucilage exuded in dry soils had a higher degree of hydrophobicity, suggesting that the wetting properties of mucilage change in response to soil drying.     

Stabilization of dissolved organic matter by sorption to the mineral soil

The main process by which dissolved organic matter (DOM) is retained in forest soils is likely to be sorption in the mineral horizons that adds to stabilized organic matter (OM) pools. The objectives of this study were to determine the extent of degradation of sorbed OM and to investigate changes in its composition during degradation. DOM of different origins was sorbed to a subsoil and incubated for 1 year. We quantified mineralized C by frequent CO₂ measurements in the headspace of the incubation vessels and calculated mean residence times by a double exponential model. Mineralization of C of the corresponding DOM in solution was used as a control to estimate the extent of DOM stabilization by sorption. Changes in the composition of sorbed OM during the incubation were studied by spectroscopic (UV, fluorescence) and isotope (¹³C, ¹⁴C) measurements after hot-water extraction of OM.The fraction of sorbed organic C mineralized during the incubation was only one-third to one-sixth of that mineralized in solution. The mean residence time of the most stable OM sample was estimated to increase from 28 years in solution to 91 years after sorption. For highly degradable DOM samples, the portion of stable C calculated by a double exponential model nearly doubled upon sorption. With less degradable DOM the stability increased by only 20% after sorption. Therefore, the increase in stability due to sorption is large for labile DOM high in carbohydrates and relatively small for stable DOM high in aromatic and complex molecules. Nevertheless, in terms of stability the rank order of OM types after sorption was the same as in solution. Furthermore, the extent of sorption of recalcitrant compounds was much larger than sorption of labile compounds. Thus, sorptive stabilization of this stable DOM sample was four times larger than for the labile ones. We conclude that stabilization of OM by sorption depends on the intrinsic stability of organic compounds sorbed. We propose that the main stabilization processes are selective sorption of intrinsically stable compounds and strong chemical bonds to the mineral soil and/or a physical inaccessibility of OM to microorganisms. The UV, fluorescence and ¹³C measurements indicated that aromatic and complex compounds, probably derived from lignin, were preferentially stabilized by sorption of DOM. The ¹³C and ¹⁴C data showed that degradation of the indigenous OM in the mineral soil decreased after sorption of DOM. We estimated DOM sorption stabilizes about 24 Mg C ha⁻¹ highlighting the importance of sorption for accumulation and preservation of OM in soil.