Phosphorus speciation of forest‐soil organic surface layers using P K‐edge XANES spectroscopy

The phosphorus (P) speciation of organic surface layers from two adjacent German forest soils with different degree of water‐logging (Stagnosol, Rheic Histosol) was analyzed by P K‐edge XANES and subsequent Linear Combination Fitting. In both soils, ≈ 70% of the P was inorganic phosphate and ≈ 30% organic phosphate; reduced P forms such as phosphonate were absent. The increased degree of water‐logging in the Histosol compared to the Stagnosol did not affect P speciation.     

Iron speciation in soils and soil aggregates by synchrotron-based X-ray microspectroscopy (XANES,μ-XANES)

Iron speciation in soils is still poorly understood. We have investigated inorganic and organic standard substances, diluted mixtures of common Fe minerals in soils (pyrite, ferrihydrite, goethite), soils in a forested watershed which constitute a toposequence with a hydrological gradient (Dystric Cambisol, Dystric Planosol, Rheic Histosol), and microsites of a dissected soil aggregate by X‐ray Absorption Near Edge Spectroscopy (XANES) at the iron K‐edge (7112 eV) to identify different Fe(II) and Fe(III) components. We calculated the pre‐edge peak centroid energy of all spectra and quantified the contribution of different organic and inorganic Fe‐bearing compounds by Linear Combination Fitting (LCF) conducted on the entire spectrum (E = 7085–7240 eV) and on the pre‐edge peak. Fe‐XANES conducted on organic and inorganic standards and on synthetic mixtures of pyrite, ferrihydrite and goethite showed that by calculating the pre‐edge peak centroid energy, the Fe(II)/Fe(III) ratio of different Fe‐bearing minerals (Fe sulphides, Fe oxyhydroxides) in mineral mixtures and soils can be quantified with reasonable accuracy. A more accurate quantification of the Fe(II)/Fe(III) ratio was possible with LCF conducted on the entire XANES spectrum. For the soil toposequence, an increased groundwater influence from the Cambisol to the Histosol was reflected in a larger contribution of Fe(II) compounds (Fe(II) silicate, Fe monosulphide, pyrite) and a smaller contribution of Fe(III) oxyhydroxides (ferrihydrite, goethite) to total iron both in the topsoil and the subsoil. In the organic topsoils, organically bonded Fe (33–45% of total Fe) was 100% Fe(III). For different microsites in the dissected aggregate, spatial resolution ofμ‐XANES revealed different proportions of Fe(II) and Fe(III) compounds. Fe K‐edge XANES andμ‐XANES allows an approximate quantification of Fe(II) and Fe(III) and different Fe compounds in soils and (sub)micron regions of soil sections, such as mottles, concretions, and rhizosphere regions, thus opening new perspectives in soil research.     

Soil sulphur speciation in two glacier forefield soil chronosequences assessed by S K‐edge XANES spectroscopy

In regions with little atmospheric input of sulphur (S) and S‐poor parent material, the bio‐availability of S, which is dependent on its speciation, may limit ecosystem production and succession. In our study, soil S speciation in two glacier forefield soil chronosequences (Hailuogou Glacier, Gongga Shan, China; Damma Glacier, Swiss Alps) was investigated for the first time. Different S species were quantified by synchrotron‐based X‐ray absorption near‐edge structure (XANES) spectroscopy at the S K‐edge. Both chronosequences show similar patterns and pedogenetic trends of their topsoil S status. Topsoil concentrations of total S were correlated with the concentrations of organic carbon and pedogenic Fe/Al oxyhydroxides. Both moraine materials contained inorganic sulphides, which in the topsoil were oxidized within 30 (Hailuogou) or 75 years (Damma) of soil development after deglaciation. About 50% of total S in the fresh moraine material at Hailuogou and 75% of that in the 15 year‐old soil at Damma was organically‐bound. During initial soil development, the contribution of organic S to total S increased at the expense of inorganic sulphide and sulphate, resulting in organic S percentages > 90% of total topsoil S after 30 (Hailuogou) and 75 (Damma) years of pedogenesis. Organic S compounds with electronic oxidation states of the S atom > + 1.5 (sulphoxides, sulphones, sulphonates and ester sulphates) dominated the organic S pool in all soils. Hence, microbial degradation of non‐sulphide organic S (sulphonates and ester sulphates) is probably important to mitigate S scarcity caused by limited availability of SO₄^2?‐S in these soils. Changes in topsoil S speciation during initial stages of pedogenesis and ecosystem succession in glacier forefields under a cool, humid climate appear to be governed by combined effects of mineral weathering (oxidation of inorganic sulphides and formation of S‐adsorbing sesquioxides), accumulation and microbial turnover of soil organic matter and the type of vegetation succession.     

Speciation of phosphorus in temperate zone forest soils as assessed by combined wet‐chemical fractionation and XANES spectroscopy

Phosphorus availability in terrestrial ecosystems is strongly dependent on soil P speciation. Here we present information on the P speciation of 10 forest soils in Germany developed from different parent materials as assessed by combined wet‐chemical P fractionation and synchrotron‐based X‐ray absorption near‐edge structure (XANES) spectroscopy. Soil P speciation showed clear differences among different parent materials and changed systematically with soil depth. In soils formed from silicate bedrock or loess, Fe‐bound P species (FePO₄, organic and inorganic phosphate adsorbed to Fe oxyhydroxides) and Al‐bound P species (AlPO₄, organic and inorganic phosphate adsorbed to Al oxyhydroxides, Al‐saturated clay minerals and Al‐saturated soil organic matter) were most dominant. In contrast, the P speciation of soils formed from calcareous bedrock was dominated (40–70% of total P) by Ca‐bound organic P, which most likely primarily is inositol hexakisphosphate (IHP) precipitated as Ca₃‐IHP. The second largest portion of total P in all calcareous soils was organic P not bound to Ca, Al, or Fe. The relevance of this P form decreased with soil depth. Additionally, apatite (relevance increasing with depth) and Al‐bound P were present. The most relevant soil properties governing the P speciation of the investigated soils were soil stocks of Fe oxyhydroxides, organic matter, and carbonate. Different types of P speciation in soils on silicate and calcareous parent material suggest different ecosystem P nutrition strategies and biogeochemical P cycling patterns in the respective ecosystems. Our study demonstrates that combined wet‐chemical soil P fractionation and synchrotron‐based XANES spectroscopy provides substantial novel information on the P speciation of forest soils.     

Phosphorus speciation in cultivated organic soils revealed by P K‐edge XANES spectroscopy

Cultivated organic soils make a significant contribution to phosphorus (P) leaching losses from agricultural land, despite occupying a small proportion of cultivated area. However, less is known about P mobilisation processes and the P forms present in peat soils compared with mineral soils. In this study, P forms and their distribution with depth were investigated in two cultivated Histosol profiles, using a combination of wet chemical extraction and P K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy. Both profiles had elevated P content in the topsoil, amounting to around 40 mmol kg^?1, and P speciation in both profiles was strongly dominated by organic P. Topsoils were particularly rich in organic P (P‐org), with relative proportions of up to 80%. Inorganic P in the profiles was almost exclusively adsorbed to surface reactive aluminium (Al) and iron (Fe) minerals. In one of the pro‐files, small contributions of Ca‐phosphates were detected. A commonly used P saturation index (PSI) based on ammonium‐oxalate extraction indicated a low to moderate risk of P leaching from both profiles. However, the capacity of soil Al and Fe to retain P in organic soils could be reduced by high competition from organic compounds for sorption sites. This is not directly accounted for in PSI and similar indices. Accumulation of P‐org in the topsoil may be attributable by microbial peat decomposition and transformation of mineral fertiliser P by both microbiota and crops. Moreover, high carbon–phosphorus ratio in the surface peat material in both profiles suggests reduced net mineralisation of P‐org in the two soils. However, advancing microbial peat decomposition will eventually lead to complete loss of peat horizons and to mineralisation of P‐org. Hence, P‐org in both profiles represents a huge potentially mobilised P pool.     

Sulfur K-edge XANES spectroscopy reveals differences in sulfur speciation of bulk soils, humic acid, fulvic acid, and particle size separates

X-ray absorption near edge structure (XANES) spectra at the sulfur (S) K-edge (E=2472 eV) were compared for bulk soil material, humic and fulvic acid fractions, and different particle size separates from Ah horizons of two arable Luvisols, from an O and a Bs horizon of a Podzol under Norway spruce forest, and from an H horizon of a Histosol (peat bog). In the bulk soil samples, the contribution of reduced organic S (organic mono- and disulfides) to total sulfur increased from 27% to 52%, and the contribution of ester sulfate and SO₄²⁻-S decreased from 39% to 14% of total S in the following order: arable Luvisols Ah—forested Podzol O—Histosol H. This sequence reflects the increasing organic carbon content and the decreasing O₂ availability in that order. Neither sulfonate nor inorganic sulfide was detected in any of the bulk soil samples. For all samples except the Podzol Bs, the XANES spectra of the bulk soils differed considerably from the spectra of the humic and acid fractions of the respective soils, with the latter containing less reduced S (16-44% of total S) and more oxidized S (sulfone S: 19-35%; ester sulfate S: 14-38% of total S). Also the S speciation of most particle size fractions extracted from the Ah horizon of the Viehhausen Luvisol and the Bs horizon of the Podzol was different from that of the bulk soil. For both soils, the contribution of oxidized S species to total S increased and the contribution of sulfoxides and organic mono- and disulfides decreased with decreasing particle size. Thus, sulfur K-edge XANES spectra of alkaline soil extracts, including humic and fulvic acids or of particle size separates are not representative for the S speciation of the original soil sample they are derived from. The differences can be attributed to (i) artificial changes of the sulfur speciation during alkaline extraction (conversion of reduced S into oxidized S, loss of SO₄²⁻ during purification of the extracts by dialysis) or particle size separation (carry-over of water-soluble S, such as SO₄²⁻), but also to (ii) preferential enrichment of oxidized S in hydrophilic water-soluble soil organic matter (ester sulfate) and in the clay fraction of soils (ester sulfate, adsorbed SO₄²⁻).     

Phosphorus in sequentially extracted fen peat soils: A K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy study

The speciation of phosphorus (P) in native and degraded peat soils is an analytical challenge, and synchrotron‐based P K‐edge X‐ray absorption near‐edge structure (XANES) is a suitable method to gain information on P species in soils and organic materials. The objective of the present study was to test if P K‐edge XANES reflected differences in P fractions in fen peat due to sequential extraction and peat degradation. We investigated each one top‐ and subsoil sample of a Fibric Histosol, which differed in the degree of humification (H8 vs. H5) and concentration of total P (P_t) (1944 mg kg^–1 vs. 436 mg kg^–1). In the topsoil, residual P, H₂SO₄‐P, and NaOH‐P accounted for roughly the same proportions of P_t (≈30%). In the subsoil, residual P (64% of P_t) was more abundant than NaOH‐P (21% of P_t) and H₂SO₄‐P (10% of P_t). Among many different P reference standards, the P XANES spectra reflected differences in mineral P more distinctive than in organic P compounds. Phosphorus XANES spectra of the residues after each sequential extraction step all showed a prominent white‐line peak at around 2152 eV. Stepwise removal of resin‐P, NaHCO₃‐P, and NaOH‐P were reflected mainly by the peak intensity but scarcely by distinct spectral features. Extraction with H₂SO₄ led to the disappearance of spectral features of Ca and Mg phosphates which is a first direct hint to these compounds in the peat. In conclusion, a combined sequential fractionation and spectroscopic (³¹P NMR, P K‐ and L‐edge XANES with linear‐combination fits) approach is proposed to overcome limitations of the present study and gain more insight into the P species in peat soils.     

The composition of mobile matter in a floodplain topsoil: A comparative study with soil columns and field lysimeters

Floodplain soils are characterized by frequent and extreme redox changes caused by inundation with river water or imbibition of groundwater. Depending on the duration and extent of inundation, biogeochemical processes run at sub‐/anoxic conditions, which may result in the mobilization and relocation of dissolved and particulate matter within the soil. In this study, we investigated the effect of inundation events on the composition of mobilized matter in the topsoil horizon of a floodplain soil. We conducted experiments with soil columns in the laboratory and gravitational lysimeters in the field to identify redox‐mediated (im)mobilization processes and to estimate their relevance under field conditions. The lysimeters were filled with topsoil monoliths and run under in situ conditions during a ≈ 2.5‐y period. The soil columns were run with the same soil material either under strictly anoxic or mixed oxic–anoxic conditions. Effluents from mixed oxic–anoxic soil were composed fundamentally different [comparably high: Mn, Al, nitrate, sulfate; comparably low: pH, organic C (OC); not detected: Fe, As] compared to effluents from strictly anoxic soil (comparably high: pH, Fe, Mn, OC, As; comparably low: Al; not detected: nitrate, sulfate). Matter, which was mobile under anoxic conditions (e.g., Fe, As, OC), was effectively immobilized as soon as the mobile phase passed anoxic–oxic boundaries within soil (exception: Mn). We assume that the solution in the soil monoliths always passed such anoxic–oxic boundaries during downwards migration independent of lysimeter flooding with river water. This is indicated by the similar composition of the lysimeter seepage water and the effluents from mixed oxic–anoxic soil columns. Both solutions contained “fingerprints” from anoxic (Mn) and oxic conditions (nitrate). Inundations with river water and the duration of these floods (1–22 d) did not affect the composition of the lysimeter seepage water. In conclusion, immediate changes in the composition of the solution, which enters either the subsoil or nearby receiving waters, cannot be expected from regular topsoil flooding.     

Quantification of chemical sulphur species in bulk soil and organic sulphur fractions by S K‐edge XANES spectroscopy

A new data treatment method for fitting spectra obtained by sulphur (S) K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy was used to quantify the chemical S speciation at three experimental sites with arable soils receiving the same long‐term field treatments. Two treatments, crop residue (CR) incorporation and farmyard manure (FYM) application, with equal applications of mineral nutrients were included in the study. In the new data treatment method, internally calibrated spectra of dilute solutions (30 mm ) of model compounds were used to fit the sample spectra. This greatly enhanced the reliability of quantitative determination of contributing S species in soil samples and soil extracts. The results indicated that long‐term FYM application shifted S species composition from highly oxidized towards intermediate oxidization in two of the soils, but in the third soil the opposite trend was observed. Sulphur XANES spectroscopy of acetylacetone extracts of physically protected and unprotected organic S in two of the soils revealed that physical protection was not related to S speciation; however, intermediate forms of oxidized S species appeared to accumulate in the residual S pool (not extractable by acetylacetone).     

Characterization of redox-related soil microbial communities along a river floodplain continuum by fatty acid methyl ester (FAME) and 16S rRNA genes

Redox states affect substrate availability and energy transformation, and, thus, play a crucial role in regulating soil microbial abundance, diversity, and community structure. We evaluated microbial communities in soils under oxic, intermittent, and anoxic conditions along a river floodplain continuum using fatty acid methyl ester (FAME) and 16S rRNA genes-based terminal-restriction fragment length polymorphism (T-RFLP) bacterial fingerprints. In all the soils tested, microbial communities clustered according to soil redox state by both evaluation techniques. Bacteria were dominant components of soil microbial communities, while mycorrhizal fungi composed about 12% of the microbial community in the oxic soils. Gram-positive bacteria consisted >10% of the community in all soils tested and their abundance increased with increasing soil depth when shifting from oxic to anoxic conditions. In the anoxic soils, Gram-positive bacteria composed about 16% of the total community, suggesting that their growth and maintenance were not as sensitive to oxygen supply as for other microbes. In general, microorganisms were more abundant and diverse, and distributed more evenly in the oxic layers than the anoxic layers. The decrease in abundance with increasing oxygen and substrate limitation, however, was considerably more drastic than the decrease in diversity, suggesting that growth of soil microorganisms is more energy demanding than maintenance. The lower diversity in the anoxic than the oxic soils was attributed primarily to the differences in oxygen availability in these soils.     

Short‐ and medium‐term evolution of soil properties in Atlantic forest ecosystems affected by wildfires

The immediate effect of low and high severity wildfires on the main soil properties, as well as their short‐ and medium‐term evolution under field conditions, was examined. The study was performed with three pine forest soils (two Leptosols and one Humic Cambisol, developed over granite and basic schist, respectively), located in the Atlantic humid temperate zone (Galicia, NW Spain). Samples were collected from the A‐horizon (0–5 cm depth) of the burnt and the corresponding unburnt soils, immediately and 3, 6 and 12 months after the wildfires. Most properties analysed exhibit immediate fire‐induced changes and different evolution depending on fire severity and soil type. In general, immediately after the fire pH and soil properties related to nutrients availability increased and cation exchange capacity decreased, whereas properties related to soil organic matter content (C, N, Fe and Al oxides) had a variable effect depending mainly on the soil studied; all these modifications were accentuated by fire severity. These effects were attenuated in the short term in the soil affected by a low severity wildfire, but they lasted for at least 1 year in the soils affected by high severity wildfires, particularly in the Leptosols. The results showed the importance of the fire as a disturbance agent in the dynamic of nutrients and soil organic matter that is directly related with soil quality in the Galician forest ecosystems. Copyright © 2011 John Wiley & Sons, Ltd.     

Soil‐phosphorus distribution and availability as affected by greenhouse subsurface irrigation

Vertical distribution and plant availability of soil P under subsurface irrigation were investigated in a 5‐year tomato‐grown‐greenhouse experiment. Irrigation was applied when soil water condition reached the predefined maximum allowable depletion (MAD) for different treatments, e.g., –10 kPa, –16 kPa, –25 kPa, –40 kPa, and –63 kPa. Results show that P distribution with soil depth was significantly affected by irrigation schedules. The general trend is that concentrations of soil total P and inorganic P were greater in topsoil than in subsoil, whereas the concentrations of soil organic P were larger at the depths of 0–10 cm, 30–40 cm, and 40–60 cm than at other soil depths. Comparison of different irrigation schedules indicates that more soil organic P was retained in the soils under the MAD of –25 kPa, –40 kPa, and –63 kPa, implying that irrigation of relatively low frequency and large water quantity of each irrigation event favored the accumulation of organic P in soils. In addition, we found that the concentrations of plant‐available P decreased with soil depth and were largest under the MAD of –16 kPa and –25 kPa. This result suggests that irrigation of relatively high frequency and low water quantity of each irrigation event led to greater P availability for plant uptake. Overall, this study suggests that the transformation and plant availability of soil P can be manipulated, to some degree, by soil‐water management. Maximum allowable depletion controlled between –16 kPa and –25 kPa could result in high availability of soil P in clay‐textured soils.     

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.     

Organic sulfur forms in mineral top soils of the Marsh in Schleswig‐Holstein,Northern Germany

Little is known about the nature of organic sulfur (S) in soils of the Marsh in Schleswig‐Holstein, Northern Germany. In addition to total and inorganic S, we determined two organic S fractions (ester sulfate‐sulfur and carbon‐bonded sulfur) in 14 aerated mineral top horizons of two salt marshes and ten dyked polder soils of different age. All soils developed from marine sediments. Total S concen‐trations ranged from 153 to 950 mg kg^—1. Organic S was the main S constituent (range from 53 to 99% with a median of 97%). Higher inorganic S levels were found only in the salt marshes due to soluble sulfate (15 to 47%). The younger marsh soils (salt marshes and soils of a polder dyked in 1978) had unique high S contents of 0.9 to 2.4% in their organic matter, whereas the S contents of the organic matter in older marsh soils were at only 0.6%. This S‐rich organic matter is a heritage of a former anoxic marine environment. In most horizons the carbon‐bonded S was the dominant sulfur form. However, both carbon‐bonded S and ester sulfate‐S did not relate to soil age. This limits the benefit of the wet chemical fractionation procedure used for studying the fate of organic S in marsh soils.     

Bodenentwicklung am Rande oligotropher Moore im Raum Berlin

Soil development in the surrounding of oligotrophic mires in the Berlin region Polygenetic soils, surrounding oligotrophic kettle hole mires in the valley and aeolian sand areas of the Berlin region, were investigated. The typical soil catena is formed by the sequence of Ombric Histosol (Niedermoor), Ombric Histosol/Albi‐gleyic Podzol (Moor‐Podsol‐Gley), Albi‐gleyic Podzol (Nasspodsol‐Gley), Gleyic Podzol (Podsol‐Gley), and Dystri‐gleyic Arenosol (Gley‐Podsol‐Braunerde) (German soil classifications in parenthesis). Field and laboratory work showed, that the investigated soils were strongly related to each other and that their development depends on the trophy of the mire and groundwater fluctuations during the Holocene. Compared with the Bh‐horizon of terrestrial soils the Gh‐horizon is nearly free of Fe and Mn, but very rich in pedogenic Al‐oxides and rich in organic matter. The genesis of the soils is explained as follows: 1. The development of different Gleyic Podzols was due to rise of groundwater. Consequently the Bh and Bs horizons of Podzols surrounding the mire were converted to Gh and Gr horizons. 2. Humic substances and Al in the Gh and Gr horizons were not re‐mobilized due to the rise of groundwater, whereas Fe and Mn were reduced and removed by groundwater. 3. At the periphery of the mire Fe was enriched in the Go horizon of the Gley‐Podzols but not Mn. 4. The fact that the mire is completely surrounded by Podzol‐Gleys, indicates, that movement of the groundwater from the central parts of mires towards the periphery is an essential pedogenetic factor.     

Respiration of nitrous oxide in suboxic soil

Reduction of nitrous oxide (N₂O) is an autonomous respiratory pathway. Nitrous oxide is an alternative electron acceptor to O₂ when intensive biological activity and reduced diffusivity result in an O₂ deficit. Hypoxic or anoxic micro sites may form even in well-aerated soils, and provide a sink for N₂O diffusing through the gas-filled pore space. We reproduced similar in vitro conditions in suboxic (0.15% O₂) flow-through incubation experiments with samples from a Stagnosol and from a Histosol. Apparent half-saturation constants ( k _m) for N₂O reduction were similar for both soils and were, on average, 3.8 μmol mol⁻¹ at 5°C, 5.1 μmol mol⁻¹ at 10°C, and 6.9 μmol mol⁻¹ at 20°C. Respiration of N₂O was estimated to contribute a maximum proportion of 1.7% to total respiration in the Stagnosol (pH 7.0) and 0.9% in the Histosol (pH 2.9).     

Nitrogen mineralization in marsh meadows in relation to soil organic matter content and watertable level

The objective of the present study was to asses the effect of watertable level on N mineralization in a Histosol and a Humic Gleysol profile under natural meadows in Ljubljana marsh, Slovenia. The two soils differ significantly in organic matter content (27—40 % in Histosol and 14—20 % in Humic Gleysol) but not in C : N ratio (13—20) and pH (6.5—7.0). For each soil, the watertable was maintained at two levels (above or below 50 cm from the soil surface) for approximately one year. The four main plots, according to soil carbon content and watertable level were divided into 4 subplots, according to 4 fertilization treatments (unfertilized control, PK, PK + 50 kg N ha^—1, PK + 3 × 50 kg N ha^—1). Net N mineralization in unfertilized subplots was estimated from indices of N mineralization obtained by incubation of soil samples in the laboratory and by seasonal dynamics of mineral N content in the field. Annual uptake of N in herbage under the 4 fertilization treatments was also measured. Total mineral N content in topsoil was 20—80 % higher in Histosol than in Humic Gleysol. Similarly, aerobic N mineralization potentials along the entire soil profile (0—90 cm) were 20—130 % higher in Histosol than in Humic Gleysol. By contrast, anaerobic N mineralization potentials in subsoil were 10—60 % lower in Histosol than in Humic Gleysol. Both, aerobic and anaerobic N mineralization potentials strongly depended on watertable levels at sampling time. Seasonal dynamics of soil mineral N content as well as N mineralization potentials indicated that the N mineralization in the Histosol could be 10—40 % higher at low than at high watertable level. In the Humic Gleysol the N mineralization could be 10—100 % higher at high watertable level. Higher N availability in Histosol at low watertable and in Humic Gleysol at high watertable was also reflected in higher N uptake in herbage. These results indicate that N mineralization in Histosol and Humic Gleysol, was proportional to soil organic matter content, whereas in both soils, higher N mineralization rates can be expected at watertable levels between 40 and 60 cm below the soil surface, than at higher/lower watertable levels.     

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.     

Effect of oxidation on the release of multiple metals from industrially polluted sediments and synchrotron-based evidence of Cu–S dynamic association

Purpose

Disposal operations for industrially polluted sediments are usually accompanied by disturbance and resuspension, which can induce metal remobilization and secondary pollution. Evaluating the risk of metal release under various redox conditions is fundamental for predicting contaminant mobilization and guiding remediation measures.

Methods

An abandoned oxidation pond, Yanjia Lake, China, was selected as a typical industrially polluted site. Re-suspension experiments were carried out by mixing polluted sediments with lake water under oxic or anoxic conditions, then investigating the effect of oxidation conditions on the release of multiple metals. Metal concentrations and aqueous chemistry in the overlying water were monitored. Synchrotron-based methods, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), were used to characterize oxidation states and coordination conditions of metals in sediments.

Results

The release of metals, including Cr, Co, Ni, Cu, Zn, Se, Mo, Sn, Cd, and Pb, was enhanced under oxic vs. anoxic conditions. The XANES analysis revealed that elevated Cr and Zn concentrations under oxic conditions likely resulted from the oxidation of Cr(III) and oxidizing dissolution of ZnS, respectively. K-edge Cu XANES, S XANES, and Cu EXAFS analyses reconstructed the Cu–S association, indicating that S-related oxidation promoted Cu release and Cu–O partly replaced Cu–S in the sediment after a 7-day oxic treatment.

Conclusion

The release of most metals was promoted under oxic conditions, resulting from the oxidation of sulfides and metals as indicated by aqueous and synchrotron-based evidence. The risk of secondary pollution is greatly enhanced under oxic conditions, which suggests that measures should be taken to minimize the redox disturbance during sediment remediation. This information can guide the management of sediments in Yanjia Lake and other contaminated sites with similar properties.

     

Phytolith‐rich biochar increases cotton biomass and silicon‐mineralomass in a highly weathered soil

Non‐essential silicon (Si) is beneficial to plants. It increases the biomass of Si‐accumulator plants by improving photosynthetic activity and alleviating stresses. Desilication, however, takes place because of natural soil weathering and removal of harvested biomass. Pyrolysis transforms Si‐rich biomass into biochar that can be used to supply bioavailable Si. Here, we applied two biochar materials differing in Si content on soils differing in weathering stage: a young Cambisol and a highly weathered Nitisol. We studied the impact of biochar supply on the bioavailability of Si, cotton biomass, and Si mineralomass. The biochar materials derived from, respectively: Miscanthus × giganteus (Mi; 34.6 g Si kg^?1 in biochar) and soft woody material (SW; 0.9 g Si kg^?1 in biochar). They were compared to conventional Si fertilizer wollastonite (Wo; CaSiO₃). Amendments were incorporated in soils at the rate of 3% (w/w). The content of bioavailable Si in soil was determined through 0.01 M CaCl₂ extraction. In the Cambisol, the proportion (CaCl₂ extractable Si: total Si content) was significantly smaller for Mi (0.9%) than for Wo (5.2%). In the Nitisol, this proportion was much larger for Mi (1.4%) than for Wo (0.7%). Mi‐biochar significantly increased Si‐mineralomass relatively to SW‐biochar in both soils. This increase was, however, much larger in the Nitisol (5.9‐fold) than in the Cambisol (2.2‐fold). Mi biochar is thus an alternative Si fertilizer to Wo to supply bioavailable Si, increase plant biomass, and promote the biological cycle of Si in the soil‐plant system in the Nitisol. Besides, it increased soil fertility and soil organic carbon content.