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.     

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.     

Availability of Organic and Inorganic Phosphorus Fractions to Wheat in Toposequences of Calcareous Soils

Abstract

Information on the availability of different soil phosphorus (P) forms is useful for crop production. Phosphorus contents of 12 Iranian calcareous soils from upper‐, mid‐, and lower‐slope positions of two arid and two semiarid toposequences were fractionated to various organic and inorganic pools, and correlations of the P fractions with wheat responses were investigated. Among the inorganic P (IP) fractions, apatite type (Ca₁₀‐P) and dicalcium phosphate equivalents (Ca₂‐P) possessed the highest and the lowest amounts of P reserve in the soils, respectively. On average, about 20% of the total P was found in organic form (OP), of which 32% was labile (LOP), 51% was moderately labile (MLOP), and 17% was nonlabile (NLOP). The amounts of the soil P fractions were considerably influenced by the positions of the soils on the landscapes. The maximum contents of soil IP, Ca₂‐P, Fe‐P (iron‐bound P), and Ca₁₀‐P were observed in the lower‐slope positions. The amount of soil available [0.5 M sodium bicarbonate (NaHCO₃) extractable] P was significantly correlated with Ca₂P (r=0.895), Fe‐P (r=0.760), and Occl‐P (iron‐occluded P) (r=0.897). Direct correlation studies, however, showed that wheat shoot dry‐matter yield (DMY) was significantly affected by the amounts of Ca₂‐P, Fe‐P, OP, LOP, and MLOP fractions both at early (4 weeks) and late (10 weeks) stages of growth. All organic and inorganic P fractions, except Al‐P (aluminum‐bound P), Ca₈‐P (octacalcium phosphate equivalents), and NLOP, also showed significant relations to the amount and/or concentration of P in wheat tissues at 4 and 10 weeks after sowing. Among the measured soil properties, the amount of organic carbon was the most affecting factor on the size of the P fractions.     

Differentiation between adsorbed and precipitated sulphate in soils and at micro-sites of soil aggregates by sulphur K-edge XANES

To investigate the potential of synchrotron‐based X‐ray Absorption Near‐Edge Structure spectroscopy (XANES) at the sulphur (S) K‐edge for a discrimination of adsorbed and precipitated sulphate in soils and soil particles, XANES spectra of ionic sulphate compounds and Al/Fe hydroxy sulphate minerals were compared with spectra of SO₄^2? adsorbed to ferrihydrite, goethite, haematite, gibbsite or allophane. Ionic sulphate and hydroxy sulphate precipitates had broader white‐lines (WL) at 2482.5 eV (full width at half maximum (FWHM) of edge‐normalized spectra, 2.4–4.2 eV; Al hydroxy sulphates, 3.0 eV) than SO₄^2? adsorbed to Al/Fe oxyhydroxides or allophane (FWHM, 1.8–2.4 eV). The ratio of the white‐line (WL) height to the height of the post‐edge feature at 2499 eV (WL/PEF) was larger for SO₄^2? adsorbed to Al/Fe oxyhydroxides or allophane (8.1–11.9) than for Al/Fe hydroxy sulphates and ionic sulphates (3.9–5.7). The WL/PEF ratio of edge‐normalized S K‐edge XANES spectra can be used to distinguish adsorbed from precipitated SO₄^2? in soils and also at microsites of soil particles. The contribution of adsorbed and precipitated SO₄^2? to the total SO₄^2? pool can be roughly quantified. Adsorbed ester sulphate may result in overestimation of precipitated SO₄^2?. The spectra of most soils could be fitted by linear combination fitting (LCF), yielding a similar partitioning between adsorbed and precipitated SO₄^2? as an evaluation of the WL/PEF ratio. The SO₄^2? pool of German forest soils on silicate parent material in most cases was strongly dominated by adsorbed SO₄^2?; however, in three German forest soils subject to elevated atmospheric S deposition, a considerable portion of the SO₄^2? pool was precipitated SO₄^2?, most likely Al hydroxy sulphate. The same is true for Nicaraguan Eutric and Vitric Andosols subject to high volcanogenic S input. In the subsoil of the Vitric Andosol, adsorbed SO₄^2? and Al hydroxy sulphate coexist on a micron scale.     

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.     

Calcium‐ and iron‐related phosphorus in calcareous and calcareous marsh soils: Sequential chemical fractionation and 31p nuclear magnetic resonance study

Abstract

Phosphorus (P) forms in soils determine the amount of P available for crops and the potential for this element to be released to water. Sequential chemical fractionation can provide some information about major P forms in soils, and allow one to distinguish iron (Fe)‐related phosphorus from calcium (Ca)‐bound P. The ³¹P nuclear magnetic resonance (NMR) spectroscopy has been used in the identification of organic P, precipitated Ca‐phosphates, and aluminum (Al)‐related P in acid soils. Three calcareous soils and four calcareous marsh soils were used in this study. These two types of soils differ in the nature of iron oxides, which are the main P sorbent surfaces. The ratio of low crystalline to high crystalline iron oxides is higher in marsh soils than in calcareous soils as a consequence of the special genesis and conditions of the soil (reduction‐oxidation cycles). Such a ratio is related to the proportion of occluded P in low crystalline oxides relative to that of high crystalline oxides. Citrate‐bicarbonate extractable P (CB‐P) in the fractionation schemes can be ascribed to adsorbed P and high soluble calcium phosphates. CB‐P is correlated with the sum of P fractions in all the soils, thus indicating that the amount of the P that can be easily released is related to the rate of P enrichment of the soil. The ³¹P NMR spectral data reveal that hydroxyapatite is the dominant P form in the soils studied. This is consistent with the fractionation data, where acid‐extractable P is the main P fraction. The spectra also provide some information about the amount of total inorganic P and Ca‐phosphates in calcareous 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.     

Bioavailability of Inorganic Phosphorus Fractions in Calcareous Soils Estimated by Neubauer Technique,Iron‐Impregnated Filter Paper,and Chemical Tests

Abstract

Plants commonly suffer from phosphorus (P) deficiency in calcareous soils. Plant responses to P application on such soils mostly show poor correlation with their soil test P values. Experiments were conducted on 24 different soil samples under laboratory and greenhouse conditions to illustrate the relationship of various inorganic P fractions in different calcareous soils with P uptake by plants, P extraction by iron‐impregnated filter paper, and P soil test values estimated by 0.5M NaHCO₃ and ammonium bicarbonate diethylene triamine penta‐acetic acid. Total P in the 24 soils ranged from 652 to 1245 mgkg^?1 with a mean of 922 mgkg^?1. A major proportion (98%) of inorganic P was in HCl‐P (Ca‐bound) form. The HCl‐P (Ca‐bound) ranged from 296 to 729 with a mean of 480 mgkg^?1. The iron (Fe) and aluminum (Al)‐P (NaOH‐P) ranged from 0.92 to 12 mgkg^?1 with a mean of 1.57 mgkg^?1. The Fe‐P (citrate‐dithionite bicarbonate) ranged from 0.22 to 4.40 mgkg^?1 with a mean of 5.99 mgkg^?1. Data regarding P release from the soil matrix obtained by desorption with iron‐impregnated filter paper was best described by the Elovich equation. Range of slope and intercept values were found to be 5.48 to 17.3 and 17.23 to 56.27 mgkg^?1, respectively. Intercept values calculated for the Elovich equation may be related to labile P initially available for plant uptake in soils. Intercept values calculated for the Elovich equation correlated (r=0.77) significantly (p<0.01) with NaHCO₃ extractable (Olsen‐P)P. Significant correlation (p<0.05) of intercept with CDB‐P (r=0.44) and of slope with HCl‐P (0.43) suggested that the initially available P, regulated through CDB‐P, is replenished by HCl‐P [calcium (Ca) bound].     

近三十年农田土壤磷分子形态的研究进展

农田土壤磷的赋存形态决定迁移、转化及归趋过程,单单通过全磷或有效磷含量并不能全面、准确、长效地评估土壤磷的养分供应能力和生态环境风险,探索可持续的农田磷素管理措施迫切需要能够科学表征、准确认识土壤磷形态。随着分析测试技术发展,农田土壤磷形态领域经历了以传统连续提取法为主的分级组分研究,到目前基于先进光谱技术的分子形态研究的发展历程。液相磷-31核磁共振技术(P-NMR)、基于同步辐射的X射线吸收近边结构谱技术(P-XANES)是当今土壤磷分子形态表征的主流技术,分别促进土壤多种有机磷和无机磷(铁磷/钙磷/铝磷)分子形态的有效识别。借助Histcite软件进行引文网络分析,梳理了近三十年(1990—2019年)土壤磷分子形态研究发展历程中具有重大借鉴意义的关键性成果,基于此综述了该领域的发展脉络,归纳发现农田土壤磷分子形态研究最初主要借助P-NMR技术侧重有机磷分子形态表征,而后过渡至与同步辐射XANES以及X射线微探针技术相结合,实现了土壤磷分子形态的全面认识。最后,对多谱学技术联用推动土壤磷分子形态研究的发展趋势进行了展望。     

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.     

Mycorrhizal (Rhizophagus Intraradices) Symbiosis and Fe and Zn Availability in Calcareous Soil

Greenhouse experiment was conducted to assess the iron (Fe) and zinc (Zn) fractionation patterns in soils of arbuscular mycorrhizal (AM) fungus-inoculated and uninoculated maize plants fertilized with varying levels of Fe and Zn. Soil samples were collected for Fe and Zn fractions and available Fe, Zn and phosphorus (P) contents besides organic and biomass carbon (BMC), soil enzymes and glomalin. Major portion of Fe and Zn fractionations was found to occur in the residual form. Mycorrhizal symbiosis increased the organically bound forms of Fe and Zn while reducing the crystalline oxide, residual Fe and Zn fractions, indicating the transformation of unavailable forms into available forms. Soil enzymes, viz. dehydrogenase and acid phosphatase activities in M+ soils, were significantly higher than M? soil consistently. Overall, the data suggest that mycorrhizal symbiosis enhanced the availability of Fe and Zn as a result of preferential fractionation and biochemical changes that may alleviate micronutrient deficiencies in calcareous soil.

Abbreviations: AM: arbuscular mycorrhiza; Fe: Iron; Zn: Zinc; P: Phosphorous; Amox-Zn: amorphous oxide bound zinc; Cryox-Zn: crystalline oxide bound zinc; DAS: days after sowing; DTPA: diethylene Triamine Penta Acetic Acid; MnO₂-Zn: manganese oxide bound zinc; OC-Zn: organically bound zinc; WSEX: water soluble plus exchangeable zinc; MnO₂ Fe: manganese oxide bound iron; OC-Fe: Organically bound iron; WSEX Fe: water soluble plus exchangeable iron.     

Phosphate Speciation and Citrate-Induced Mobilization of P in an Acric Oxisol

Billions of dollars are spent annually in Brazil on imported phosphorus (P) fertilizers for agricultural crops produced on Oxisols. Phosphate fixation by Oxisols is a main limitation to crop productivity because these highly weathered soils have a high phosphate adsorption capacity. The objective was to determine whether reaction of an Acric Oxisol with citrate increases P availability. Columns of P-amended subsoil material were leached with 1 mM citrate solution, and effluent was monitored. Solid-phase speciation was measured for different stages of leaching using X-ray absorption near edge structure (XANES) spectroscopy at the P K-edge. When soil columns were leached with up to 56 column pore volumes of 1 mM citrate solutions, no P was detected in column effluent samples, whereas aluminum (Al) and iron (Fe) increased up to 30 and 1.4 µmol L^?1, respectively. The XANES analysis suggested that with increased leaching, a minor proportion of phosphate adsorbed on Fe-oxides increased as phosphate adsorbed on Al-oxides decreased. The results indicated that citrate tends to induce minor species redistribution of phosphate between Al- and Fe-oxide bound forms, but P mobilization was trivial compared with complexometric mobilization of Fe and Al.     

Underestimation of Available Phosphorus by Resin–Bicarbonate and Olsen Tests in Calcareous Soils treated with Gypsum

In the present study, Olsen [0.5 M sodium bicarbonate (NaHCO₃), pH 8.5] and resin–bicarbonate (HCO₃) tests underestimated available phosphorus (P) in calcareous soils treated with gypsum (CaSO₄). The reaction of CaSO₄ and HCO₃ ^? ion or resin–HCO₃ to form calcium carbonate (CaCO₃) precipitate reduced the strength of the Olsen NaHCO₃ extractant and resin–HCO₃ strip for P extraction. The iron (Fe) oxide–impregnated filter paper (Pi strip) was independent of CaSO₄ influence and thus correctly estimated soil‐available P with respect to plant response to soil‐available P. Two greenhouse experiments were conducted with maize and wheat grown on calcareous soils treated with different rates of CaSO₄. The results confirmed that Olsen and resin–HCO₃ tests should not be used to measure available P or labile P in the P fractionation scheme in the calcareous soils containing significant amounts of gypsum.     

Phosphorus sorption,supply potential and availability in soils with contrasting parent material and soil chemical properties

Soil phosphorus (P) management requires a more targeted and soil‐specific approach than is currently applied for agronomic recommendations and environmental evaluation. Phosphorus buffering capacities control the supply of P in the soil solution and were measured across Irish soils with contrasting parent material and chemical properties. Langmuir sorption buffer capacities (MBCs) and binding energies (b) were strongly correlated with soil pH and extractable aluminium (Al). A broken‐line regression fitted to the relationship between MBC and Al derived a change‐point value for Al above which MBC increased linearly. Soils above the change point were predominantly acidic to neutral with non‐calcareous parent material, with larger buffering capacities and binding energies than calcareous soils. Ratios of Mehlich3‐Al and P (Al:P) were used to relate buffering capacity to supply potential in non‐calcareous soils. Large ratios of Al:P were associated with poor P availability, characteristic of strongly P‐fixing soils. Threshold values of iron‐oxide paper strip P (FeO‐P) and Morgan's P revealed Al:P ratios where soils began to supply P in available form. The change‐point for Morgan's P fell within the current target index for P availability; however, the confidence interval was more compatible with previous agronomic P indices used in Ireland. Relationships between Morgan's P and measures of extractable P, M3‐P and Olsen P, deviated in calcareous soils at large soil P contents, indicative of P precipitation processes dominating in these soils. Identifying differences in soil P buffering capacity at the laboratory scale would improve agronomic and environmental assessment at field and catchment scales.     

Impact of Soil Sorption Characteristics and Bedrock Composition on Phosphorus Concentrations in two Bohemian Forest Lakes

Phosphate (PO₄-P) sorption characteristics of soils and bedrock composition were determined in catchments of two mountain lakes, Ple?né Lake (PL) and ?ertovo Lake (CT), situated in the Bohemian Forest (Czech Republic). The aim was to explain higher terrestrial P export to mesotrophic PL compared to oligotrophic CT. Concentrations of Al and Fe oxides were the dominant parameters affecting soil ability to adsorb PO₄-P. Depending on concentrations of Al and Fe oxides, P sorption maxima varied from 9.7 to 70.5 mmol kg^?1 and from 7.4 to 121 mmol kg^?1 in organic and mineral soil horizons, respectively. The catchment weighted mean PO₄-P sorption capacity was 3.4 mol m^?2 and 11.9 mol m^?2 in the PL and CT soils, respectively. The higher PO₄-P sorption capacity in the CT catchment was predominantly associated with higher pools of soil and Fe oxides. The CT bedrock (mica schist) released one order of magnitude less P than the PL bedrock (granite) within a pH range of catchment soils (pH_CaCl2 of 2.5–4.5). The higher ability of PL bedrock to release P and the lower ability of PL soils to adsorb PO₄-P thus contributed to the higher terrestrial P loading of this lake.     

Long‐term tillage effects on the distribution of phosphorus fractions of loess soils in Germany

Different tillage systems may affect P dynamics in soils due to differently distributed plant residues, different aggregate dynamics and erosion losses, but quantitative data are scarce. Objectives were to investigate the effect of tillage on the availability of P in a long‐term field trial on loess soils (Phaeozems and Luvisols) initiated from 1990 to 1997. Four research sites in E and S Germany were established with a crop rotation consisting of two times winter wheat followed by sugar beet. The treatments were no‐till (NT) without cultivation, except for seedbed preparation to a depth of 5 cm before sugar beet was sown and conventional tillage (CT) with mouldboard plowing down to 25–30 cm. Soil P was divided into different pools by a sequential extraction method, and total P (P_t) in the single P fractions was extracted by digesting the extracts of the fractionation to calculate the contents of organic P. The P_t content (792 mg [kg soil]^–1) in the topsoil (0–5 cm) of NT was 15% higher compared to CT, while with increasing depth the P_t content decreased more under NT than under CT. This was also true for the other P fractions except for residual P. The higher P contents in the topsoil of NT presumably resulted from the shallower incorporation of harvest residues and fertilizer P compared to CT, whereas estimated soil losses and thus also P losses due to water erosion were only small for both treatments. Contents of oxalate‐extractable Fe and organic C were positively related to the labile fractions of inorganic P, while there was a high correlation of the stable fractions with the clay contents and pH. Multiple regression analyses explained 50% of the variability of these P fractions. Overall, only small differences in the P fractions and availability were observed between the long‐term tillage treatments.     

Availability of soil boron fractions to M.26 apple rootstock

The availability of various boron (B) fractions in soil to M.26 apple (Malus spp.) rootstock was examined. The study was carried out in a greenhouse on soils with diverse chemical and physical properties. The following B fractions were determined: (i) B in soil solution, (ii) B non‐specifically adsorbed on soil surface, (iii) B specifically adsorbed on soil colloid surfaces, (iv) B occluded in Mn oxyhydroxides, (v) B occluded in noncrystalline aluminum (Al) and iron (Fe) oxides, (vi) B occluded in crystalline Al and Fe oxides, (vii) B fixed with soil silicates, and (viii) total soil B. In the studied soils there were: 0.07–0.17 mg kg^‐1 B in soil solution, 0.01–0.03 mg kg^‐1 B non‐specifically adsorbed on soil surface, 0.04–0.08 mg kg^‐1 B specifically adsorbed on soil colloid surfaces, 0.28–0.67 mg kg^‐1 B occluded in manganese (Mn) oxides, 4.03–17.22 mg kg^‐1 B occluded in noncrystalline Al and Fe oxides, 8.93–50.62 mg kg^‐1 B occluded in crystalline Al and Fe oxides, 12.2–42.5 mg kg^‐1 B fixed with soil silicate, and 52.9–82.2 mg kg^‐1 total B. Simple correlation analysis showed positive correlation between B contents in M.26 apple rootstocks and amounts of B in soil solution (r=0.77), B non‐specifically adsorbed on soil colloid surfaces (r=0.65), B specifically adsorbed on soil surface (r=0.76) and B occluded in Mn oxyhydroxides (r=0.77). No relation was found between plant B contents and amounts of B occluded in non‐crystalline and crystalline Al and Fe oxides, B fixed with soil silicates and total B. The results indicated that extraction of B by 0.1 M NH₂OH HCl solution adequately represented amounts of B in soil solution, B non‐specifically and specifically adsorbed on soil compound surfaces and B occluded in Mn oxyhydroxides to assess availability of B to apple trees.     

Sequentially extracted phosphorus fractions in peat‐derived soils

Phosphorus (P) forms were sequentially extracted from peat derived soils (Eutric Histosols and Gleysols) at eight sites in Saxony‐Anhalt (Germany) to disclose general differences in P pools between mineral and organic soils and to investigate effects of peat humification and oxidation in conjunction with land use and soil management on the P status of soils. Overall 29 samples providing a wide variety of basic chemical properties were subjected to the Hedley fractionation. The Histosol topsoils contained more total P (P_t) (1345 ± 666 mg kg^—1) than the Gleysol topsoils (648 ± 237 mg kg^—1). The predominant extractable fractions were H₂SO₄‐P (36—63 % of P_t) in calcareous and NaOH‐P_o (0—46 % of P_t) in non‐calcareous Histosols. These soils had large pools of residual P (13—93 % of P_t). Larger contents and proportions of P_o and of labile P fractions generally distinguished organic from mineral soils. Regression analyses indicated that poorly crystalline pedogenic oxides and organic matter were binding partners for extractable and non‐extractable P. Intensive management that promotes peat humification and oxidation results in disproportional enrichments of labile P fractions (resin‐P, NaHCO₃‐P_i, and NaHCO₃‐P_o). These changes in P chemistry must be considered for a sustainable management of landscapes with Histosols and associated peat derived soils.     

Inorganic Phosphorus Fractionation of Highly Calcareous Soils of Iran

Abstract

Highly calcareous soils are abundant in Iran. The calcium carbonate equivalent (CCE) of these soils reach up to 650 g kg^?1. Although phosphorus (P) fertilizer is being widely used in these soils, little information, if any, is available about P status in such soils. The objectives of this study were to 1) determine inorganic P forms in 18 surface soils of southern Iran, 2) study P readsorption during different stages of fractionation schemes, 3) assess the ability of NaOH to extract aluminum (Al)‐P, and 4) evaluate the relationships between P availability indices and inorganic P forms. Eighteen soil samples with a wide range of physicochemical properties were selected for this study. Inorganic P forms was determined by sequential extraction with NaHCO₃, NH₄OAc, NH₄F, NaOH, citrate dithionite (CD), and H₂SO₄, which are referred to as Ca₂‐P, Ca₈‐P, Al‐P, Fe‐P, occluded P (O‐P), and Ca₁₀‐P. Phosphorus readsorption in different stages was determined by 1 M MgCl₂. Furthermore, a fractionation scheme without an NH₄F step was used to evaluate the ability of NaOH to extract Al‐P. NaHCO₃ (Olsen‐P) and MgCl₂‐extractable P (Exch‐P) were regarded as P-availability indices. The abundance of different P forms was in the order Ca₂‐P<Fe‐P<Al‐P<O‐P<Ca₈‐P<Ca₁₀‐P. Ca₂‐P was highly correlated with Olsen‐P and Exch‐P. Ca₂‐P, Olsen‐P, and Exch‐P showed a relationship with CCE, citrate–bicarbonate–dithionite extractable Fe (Fe_d), and Al (Al_d). Phosphorus readsorption appeared to be important only in the Ca₈‐P step, and the content of readsorbed P was related to Ca₈‐P, CCE, and clay content of the soils. In the present study, Al‐P and Fe‐P accounted for 10 and 5% of the sum of the inorganic P fractions, respectively, and Fe‐P showed a strong relationship with Fe_o, whereas Al‐P showed a significant relationship with oxalate‐extractable Al (Al_o) and Al_d. It was found that one extraction with NaOH is not a good indicator for Fe‐ and Al‐P, and the ability of NaOH to extract Al‐P was reduced with increase in Al‐P content.     

Phosphorus pools in soil after land conversion from silvopasture to arable and grassland use

Differences in soil P among silvopasture, grassland, and arable lands have been well established. Nevertheless, most of the reports compare soil properties under long‐term sites. Thus, there exists little information on the effect of the conversion of silvopasture to arable or grassland use on soil P pools. The objective of the study was to determine the impact of converting silvopasture system (SP) into arable cropping and grassland system on the distribution of P pools and potential P bioavailability. We compared the following systems: SP system, SP converted to arable cropland (SP‐AL), SP converted to grassland (SP‐GL), and for comparative purposes, a long‐term arable cropland (AL). The P fractionation was performed by a sequential extraction scheme, using acid and alkaline extractants on samples collected from the 0–10 and 10–20 cm soil layers. It was assumed that the large variations in soil‐P fractionations are caused by the different management practices associated with land conversion. The results of P fractionation showed a dominance of calcium‐bound P, HCl‐extractable Pi constituted up to 36% of the soil total P (TP). However, the type of land use did not affect this P fraction. On the other hand, the reduction in labile‐P_i and NaOH‐P_i fractions observed at the SP‐AL site may have led to the decline in readily available P. The soil total organic P (TP_o) content was 8% and 17% lower at SP‐AL compared to SP and SP‐GL site, respectively. Labile organic‐P (labile‐P_o) content was markedly higher at SP site compared to arable soils, and was ≈ 10% of TP_o. The NaOH‐P_o constituted the highest fraction of the organic‐P pool (55%–79% of TP_o) across all the study systems, and was positively correlated with TP_o (p < 0.01). The study indicates that conversion of SP system in temperate regions to arable cropping with conventional tillage seems to result in the reduction of P availability compared to SP, indicating SP as an important land‐use practice.