Land-use and fertilization effects on P forms in two European soils: resin extraction and 31P-NMR analysis

Macroporous anion-exchange resin extraction and ³¹P-NMR spectroscopy of dialysed NaOH extracts were used to investigate the effects of land use (Taubenberg, Bavaria: spruce forest, deciduous forest, permanent grass, arable) and fertilization (Askov, Denmark: unmanured, mineral fertilizer, animal manure) on forms of phosphorus in soil with emphasis on the potentially labile organic (P_o) and inorganic (P_i pools. Carbon content ranged from 12.5–118.1 g kg^?1 and total P (P_i) content from 511 to 2063 mg kg^?1. For all soils, the C:P_o ratios of SOM decreased in the order: whole soil, 150: 1–44:1; alkali extract, 57:1–41: 1; resin extract, 20:1–9:1; suggesting an increasing P functionality of the OM with increasing P_o lability. Analysis of functional relation showed a close relation between resin P_o and ³¹P-NMR estimates for diester-P including teichoic acid-P, indicating that these species contributed significantly to the labile P_o pool as determined by the resin method. The most marked effects of land-use were an increase in P_i under grass and arable, a concurrent sequestration of P_o and SOM under grass, and a depletion of P_o under arable. The amount of resin P_j appeared to be a function primarily of fertilization, and amounted to around 100 mg kg^?1 in the fertilized soils irrespective of the SOM content and P source. The forest soil and the unfertilized agricultural soil had much smaller resin P_j values. The soil under grass had the largest amounts in resin P_o and diester-P including teichoic acid-P, indicating a rapid turnover of P_o with build-up of a large potentially labile, microbially derived P_o pool. ³¹P NMR also showed large proportions of labile P_o species in soils where microbial activity is restrained by acidity (Taubenberg spruce forest, phosphonates) or where highly microbially altered OM is relatively enriched (Taubenberg arable, diester-P including teichoic acid-P). We conclude that the resin used in this study isolates a structurally and functionally reasonably uniform pool of potentially labile soil P_o.     

Desorption of myo‐inositol hexakisphosphate and phosphate from goethite by different reagents

Inositol phosphates are abundant organic phosphates found widely in the environment. The sorption and desorption of organic phosphate (P_o) are important processes in controlling the mobility, bioavailability and fate of phosphorus (P) in soil and sediment. The desorption characteristics of myo‐inositol hexakisphosphate (IHP) and inorganic phosphate (P_i) from goethite were studied by pre‐sorption of IHP or P_i followed by desorption by KCl, H₂O, and citrate. Batch experiments and in situ attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy were used to investigate the desorption of IHP/P_i. The desorption percentage of IHP/P_i by citrate was much higher than that by H₂O/KCl. The desorption of P by citrate was mainly achieved through ligand exchange, and the desorption increased with decreasing pH. Desorption by H₂O was slightly greater than that by 0.02 M KCl because the electrostatic repulsion between the P molecules is larger in H₂O. Due to the higher affinity of IHP for goethite than that of P_i, the maximum desorption of IHP was lower than that of P_i. Desorption curves (desorption concentration in solution vs. sorption density) of IHP or P_i on goethite by KCl or H₂O was well fitted by an exponential equation, while those by citrate were well fitted by a linear equation. The desorption amounts of P in the first cycle account for more than 58% of the total desorption followed by substantial decreases in the second and third cycles. There was a re‐sorption of P_i from solution in the late stage of desorption by KCl and H₂O, resulting in a sharp decrease in desorption. Re‐sorption of IHP did not occur, which is probably due to its poor diffusion into goethite. The initial desorption rate of P_i with KCl and H₂O decreased with increasing pre‐sorption time, whereas that of IHP was opposite. This study indicates that strong sorption on and weak desorption of IHP from iron (hydr)oxides may explain the accumulation of IHP in soils.     

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‐31–nuclear magnetic–resonance spectroscopy to trace organic dung phosphorus in a temperate grassland soil

Cattle dung contributes to hot‐spot inputs of nutrients to grassland systems, but not much is known about its organic P (P_o) composition and fate in the grassland soils. We used ³¹Phosphorus (P)–Nuclear Magnetic–Resonance (NMR) spectroscopy of alkaline soil extracts to examine potentials for tracing of different functional P_o forms into a temperate grassland soil amended with dung. The proportion of monoester, DNA‐diester, and phospholipid+teichoic acid P were comparable in dung extracts, but the soil was dominated by monoester P. The temporal trends in the DNA‐diester P–to–monoester P (D_DNAM) and diester P–to–monoester P (DM) ratio of dung, native soil, and soil amended with dung were monitored in the 70 d field experiment. The D_DNAM and DM ratio in the dung‐amended soil (0–1 and 1–5 cm depth) were always intermediate between the dung and (unamended) control soil. Clearly, extracted soil P was a mixture of incorporated dung‐derived P and native soil P. The dung‐P contribution in the 0–1 cm samples peaked at 47% of the total extracted P at day 70 and at 15% after 42 d in the 1–5 cm soil depth (based on the DM ratio). The proportions of dung‐derived P and C in the soil were positively correlated with: 1) topsoil, using the D_DNAM ratio (r² = 0.975), and 2) top‐ and subsoil, using the DM ratio (r² = 0.656). We concluded that our D_DNAM and DM‐P ratios approach (obtained from solution‐³¹P NMR) did trace successfully the short‐term dynamics and fate of dung P_o in soil. It indicated that dung‐derived P_o varied as rapidly in soil as the dung‐derived C.     

Soil phosphorus dynamics in a Vertisol as affected by cattle manure and nitrogen fertilization in soybean‐wheat system

Repeated application of phosphorus (P) as superphosphate either alone or in conjunction with cattle manure and fertilizer N may affect the P balance and the forms and distribution of P in soil. During 7 years, we monitored 0.5 M NaHCO₃ extractable P (Olsen‐P) and determined the changes in soil inorganic P (P_i) and organic P (P_o) caused by a yearly dose of 52 kg P ha^—1 as superphosphate and different levels of cattle manure and fertilizer N application in a soybean‐wheat system on Vertisol. In general, the contents of Olsen‐P increased with conjunctive use of cattle manure. However, increasing rate of fertilizer nitrogen (N) reduced the Olsen‐P due to larger P exploitation by crops. The average amount of fertilizer P required to increase Olsen‐P by 1 mg kg^—1 was 10.5 kg ha^—1 without manure and application of 8 t manure reduced it to 8.3 kg ha^—1. Fertilizer P in excess of crop removal accumulated in labile (NaHCO₃‐P_i and P_o) and moderately labile (NaOH‐P_i and P_o) fractions linearly and manure application enhanced accumulation of P_o. The P recovered as sum of different fractions varied from 91.5 to 98.7% of total P (acid digested, P_t). Excess fertilizer P application in presence of manure led to increased levels of Olsen‐P in both topsoil and subsoil. In accordance, the recovery of P_t from the 0—15 cm layer was slightly less than the theoretical P (P added + change in soil P — P removed by crops) confirming that some of the topsoil P may have migrated to the subsoil. The P fractions were significantly correlated with apparent P balance and acted as sink for fertilizer P.     

Soil organic matter stabilization in acidic forest soils is preferential and soil type-specific

Minerals with large specific surface areas promote the stabilization of soil organic matter (SOM). We analysed three acidic soils (dystric, skeletic Leptic Cambisol; dystric, laxic Leptic Cambisol; skeletic Leptic Entic Podzol) under Norway spruce (Picea abies) forest with different mineral compositions to determine the effects of soil type on carbon (C) stabilization in soil. The relationship between the amount and chemical composition of soil organic matter (SOM), clay content, oxalate‐extractable Fe and Al (Fe_o; Al_o), and dithionite‐extractable Fe (Fe_d) before and after treatment with 10% hydrofluoric acid (HF) in topsoil and subsoil horizons was analysed. Radiocarbon age, ¹³C CPMAS NMR spectra, lignin phenol content and neutral sugar content in the soils before and after HF‐treatment were determined and compared for bulk soil samples and particle size separates. Changes in the chemical composition of SOM after HF‐treatment were small for the A‐horizons. In contrast, for B‐horizons, HF‐soluble (mineral‐associated) and HF‐resistant (non‐mineral‐associated) SOM showed systematic differences in functional C groups. The non‐mineral associated SOM in the B‐horizons was significantly depleted in microbially‐derived sugars, and the contribution of O/N‐alkyl C to total organic C was less after HF‐treatment. The radiocarbon age of the mineral‐associated SOM was younger than that of the HF‐resistant SOM in subsoil horizons with small amounts of oxalate‐extractable Al and Fe. However, in horizons with large amounts of oxalate‐extractable Al and Fe the HF‐soluble SOM was considerably older than the HF‐resistant SOM. In acid subsoils a specific fraction of the organic C pool (O/N‐alkyl C; microbially‐derived sugars) is preferentially stabilized by association with Fe and Al minerals. Stabilization of SOM with the mineral matrix in soils with large amounts of oxalate‐extractable Al_o and Fe_o results in a particularly stable and relatively old C pool, which is potentially stable for thousands of years.     

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.     

Effect of long‐term fertilization on the transformations of water‐extractable phosphorus in a fluvo‐aquic soil

Improved information on water‐extractable soil P (P_w) and its distribution in various forms is needed to assess its bioavailability and environmental impact. This study investigated P_w in a fluvo‐aquic soil solution in relation to the continuous application of inorganic fertilizer (NPK) and wheat straw–soybean‐based compost for 15 y. Phosphatase‐hydrolysis techniques were used to fractionate organic P (P_o) in water extracts of soil into phosphomonoester (P_om) and phosphodiester (P_od). In comparison with the noncomposted treatments, compost application significantly increased the levels of inorganic P (P_i) and P_o. P_om was the main form in water‐extractable soil P_o (71%–88%), in which sugar phosphate (P_os) occupied 48%–75%, inositol hexakisphosphate (P_op) comprised 13%–23%, and P_od only accounted for a small percentage (11%–26%). Long‐term compost application significantly increased the content of P_om, P_os, and P_od, but decreased the P_op content; the ratio of P_om to P_o increased significantly in compost‐treated soil, but the ratio of P_op to P_o and P_od to P_o significantly decreased. Thus, the equilibrium of phosphatase involved P transformations shifted to P_i in compost‐treated soil. The phosphomonoesterase and phosphodiesterase activities were significantly higher in compost‐treated soil, which favored the transformations of P_od into P_om and P_om into P_i. The ratio of P_o to P_w in water extracts of compost‐treated soil was similar to that of control soils with no fertilizer input (CK), but was significantly lower than in NPK treatment, which demonstrated that a larger increase occurred for soil P_i in water extracts of compost‐treated soil. Long‐term compost application in the fluvo‐aquic soil changed the composition of P_w, promoted the rate of P transformations in soil solution, and significantly increased soil P bioavailability.     

Organic matter stabilization in two Andisols of contrasting age under temperate rain forest

Recent studies with Andisols show that the carbon (C) stabilization capacity evolves with soil age relative to the evolution of the mineral phase. However, it is not clear how soil mineralogical changes during pedogenesis are related to the composition of soil organic matter (SOM) and ¹⁴C activity as an indicator for the mean residence time of soil organic matter (SOM). In the present study, we analyzed the contribution of allophane and metal–SOM complexes to soil C stabilization. Soil organic matter was analyzed with solid-state ¹³C nuclear magnetic resonance spectroscopy. Additionally, the soil was extracted with Na-pyrophosphate (Al_p, Fe_p) and oxalate (Al_o, Si_o, and Fe_o). Results supported the hypothesis that allophane plays a key role for SOM stabilization in deep and oldest soil, while SOM stabilization by metal (Al and Fe) complexation is more important in the surface horizons and in younger soils. The metal/C_p ratio (C_p extracted in Na-pyrophosphate), soil pH, and radiocarbon age seemed to be important indicators for formation of SOM–metal complexes or allophane in top- and subsoils of Andisols. Changes in main mineral stabilization agents with soil age do not influence SOM composition. We suggest that the combination of several chemical parameters (Al_p, Fe_p and C_p, metal/C_p ratio, and pH) which change through soil age controls SOM stabilization.     

The role of non‐crystalline Fe in the increase of SOC after long‐term organic manure application to the red soil of southern China

Because of the important role of soil organic carbon (SOC) in nutrient cycling and global climate changes, there has been an interest in understanding how different fertilizer practices affect the SOC preservation and promotion. The results from this study showed that long‐term application of manure (21 years) could increase significantly the content of SOC, total nitrogen (N) and soil pH in the red soil of southern China. The chemical structure of SOC was characterized by using solid‐state cross‐polarization magic angle spinning (CPMAS) ¹³C nuclear magnetic resonance (NMR) spectroscopy, and the aromatic C, ratio of alkyl C : O‐alkyl C, aromaticity and hydrophobicity of mineral fertilizers N, P and K plus organic manure (NPKM) and organic manure (M) treatments were less than those of mineral fertilizer nitrogen (N) and mineral fertilizers N, P and K (NPK) treatments. Both poorly crystalline (Fe_o) and organically complexed (Fe_p) iron contents were influenced significantly (P < 0.05) by different fertilizers, and it was observed that NPKM and M treatments increased the non‐crystalline Fe (Fe_o‐Fe_p) content. There was a significant (P < 0.01) positive correlation between soil organic C and non‐crystalline Fe in both the surface (0–20 cm) and subsurface (20–40 cm) soils. The results suggested that non‐crystalline Fe played an important role in the increase of SOC by long‐term application of organic manure (NPKM and M) in the red soil of southern China.     

Phosphorus Source Effects on Soil Organic Phosphorus: A 31P NMR Study

The nature of organic phosphorus (P_o) in animal waste and in soil is important from both plant nutrition and environmental perspectives. The objectives of this study were (1) to monitor the nature of P_o in different animal wastes and biosolids using solution state ³¹P NMR spectroscopy and (2) to understand the nature of P_o as affected by crop P removal in soil amended with different animal wastes and biosolids under greenhouse conditions. Two types of stockpiled cattle (Bos taurus) manure (CM1 and CM2), solid turkey (Meleagris gallopava) litter (TL), solid hog (Sus scrofa) manure (HM), and aerobically digested biosolids (SS) were used. Two kg of Wabash silt loam soil was amended with 0 or 150 mg P kg^?1 from the P sources. Seven harvests of corn (Zea mays L.) were collected, each 35 days after sowing. Organic P was extracted with 0.4 M NaOH from soil samples collected before cropping and after the seventh harvest, as well as from each P source. ³¹P NMR analysis suggested that sugar phosphomonoester was present in all P sources and was the dominant constituent of both CM1 and CM2. Phosphomonoester was detected in large amounts in TL, HM, and SS. Prior to crop P removal, the application of all P sources caused the relative content of sugar phosphomonoester to be greater than the control. Crop P removal resulted in reductions in the relative content of sugar phosphodiesters and phosphodiester in CM1‐ and CM2‐amended soils, respectively. Phosphomonoester was also decreased in TL‐, HM‐, and SS‐amended soils in response to cropping.     

Resin extraction of labile, soil organic phosphorus

In order to develop a method for estimating labile, soil organic phosphorus (P_o), macroporous anion-exchange and adsorbent (XAD) resins were tested for their ability to extract P_o from a permanent pasture soil. Experimental variables included: ionic form, soil-water resin ratio, addition of cation-exchange resin, extraction time, extraction temperature, continuous and stepwise extraction and soil pretreatment (chloroform and microwaves). The amounts of extracted P_o and P_i (inorganic phosphorus) showed little variation between the anion-exchange resins, when used in the bicarbonate form. In the chloride form, the amounts extracted were less and more variable. XAD resins extracted much less P_o and very little P_i. The macroporous anion-exchange resin, Lewatit MP500A in the bicarbonate form, was chosen for further studies. It extracted 21 mg P_o kg^?1 from air-dried soil and 8 mg P_o kg^?1 from moist, incubated soil. The specific amounts of P_o and P_i extracted were little affected by variations in the ratio between soil, water and resin, but increased with extraction time and temperature. Chloroform pretreatment of the soil mainly increased extracted P_i, whereas microwave pretreatment only increased extracted P_o. The magnitude of these increases was approximately constant irrespective of extraction temperature, indicating that the increases came from killed micro organisms.     

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.     

Soil organic phosphorus in tropical forests: an assessment of the NaOH–EDTA extraction procedure for quantitative analysis by solution 31P NMR spectroscopy

The extraction of soil organic phosphorus by the NaOH–EDTA procedure was assessed in detail for a tropical forest soil (clay‐loam, pH 4.3, total carbon 2.7%). Optimum conditions for the quantification of soil organic phosphorus and characterization of its composition by solution ³¹P NMR spectroscopy were extraction in a solution containing 0.25 m NaOH and 50 mm Na₂EDTA in a 1:20 solid to solution ratio for 4 hours at ambient laboratory temperature. Replicate analyses yielded a coefficient of variation of 3% for organic phosphorus as a proportion of the spectral area. There was no significant difference in total phosphorus extraction from fresh and air‐dried soil, although slightly more organic phosphorus and less paramagnetic ions were extracted from dried soil. The procedure was not improved by changing the concentration of NaOH or EDTA, extraction time, or solid to solution ratio. Pre‐extraction with HCl or Na₂EDTA did not increase subsequent organic phosphorus extraction in NaOH–EDTA or improve spectral resolution in solution ³¹P NMR spectroscopy. Post‐extraction treatment with Chelex resin did not improve spectral resolution, but removed small concentrations of phosphorus from the extracts. Increasing the pH of NaOH–EDTA extracts (up to 1.0 m NaOH) increased the concentration of phosphate monoesters, but decreased DNA to an undetectable level, indicating its hydrolysis in strong alkali. The standardized NaOH–EDTA extraction procedure is therefore recommended for the analysis of organic phosphorus in tropical forest soils.     

Decadal Nitrogen Fertilization Decreases Mineral‐Associated and Subsoil Carbon: A 32‐Year Study

Crop residues and manure are important sources of carbon (C) for soil organic matter (SOM) formation. Crop residue return increases by nitrogen (N) fertilization because of higher plant productivity, but this often results only in minor increases of SOM. In our study, we show how N fertilization and organic C additions affected SOM and its fractions within a 32‐year‐long field‐experiment at Puch, Germany. Five organic additions, no‐addition (control), manure, slurry, straw and straw + slurry, were combined with three mineral N fertilization rates (no, medium and high fertilization), which resulted in 1·17–4·86 Mg C‐input ha^‐1 y^‐1. Topsoil (0–25 cm) SOM content increased with N fertilization, mainly because of the C in free light fraction (f‐LF). In contrast, subsoil (25–60 cm) SOM decreased with N fertilization, probably because of roots' relocation in Ap horizon with N fertilization at the surface. Despite high inputs, straw contributed little to f‐LF but prevented C losses from the mineral‐associated SOM fraction (ρ > 1·6 g cm^‐3) with N fertilization, which was observed without straw addition. Above (straw) and belowground (roots) residues had opposite effects on SOM fractions. Root C retained longer in the light‐fractions and was responsible for SOM increase with N fertilization. Straw decomposed rapidly (from f‐LF) and fueled the mineral‐associated SOM fraction. We conclude that SOM content and composition depended not only on residue quantity, which can be managed by the additions and N fertilization, but also on the quality of organics. This should be considered for maintaining the SOM level, C sequestration, and soil fertility. Copyright © 2016 John Wiley & Sons, Ltd.     

Evaluation of the factors affecting direct polarization solid state 31P-NMR spectroscopy of bulk soils

³¹P‐NMR spectroscopy on bulk soils is a powerful tool for the identification of the different phosphorus forms in soils and for the evaluation of the dynamics of soil P. Up to now the majority of the papers dealt with liquid state ³¹P‐NMR spectroscopy on soluble soil organic substances. Only few papers were addressed to the study of the different phosphorus forms directly in bulk soils. In the present paper, some organic and inorganic phosphates of known structures, which are likely to be present in soil systems, were studied by direct polarization (DP) magic angle spinning (MAS) ³¹P‐NMR spectroscopy in order to understand the electronic factors responsible for chemical shifts of the phosphorus (P) nucleus and to serve as guidelines to assign P resonances in soil spectra. Number of hydrating water molecules, type of counter‐cation, degree of covalence, and spatial conformation of P in phosphate structures were found to affect signal positions in ³¹P‐NMR spectra. Both hydrating water and increase in degree of covalence of the X‐O‐P bonds (X=H, Na) enhanced the electronic density (E_D) around P, thereby producing up‐field shifts in ³¹P‐NMR spectra. The exchange of the Na⁺ counter‐cation with NH₄⁺ resulted in an increase of the cation potential (P_C) that is a measure of the cation polarizing power, and induced a down‐field shift of P signals, due to a corresponding reduction in E_D around the P nucleus. Both NMR down‐ and up‐field shifts were observed in organic phosphates, and were dependent on the spatial orientation of the phosphate groups that may have been fixed anisotropically in the solid state. Based on the factors that influence P chemical shifts for standard phosphates, attempts to assign ³¹P‐NMR signals in the spectra of five different unperturbed bulk soils were made.     

Distribution of phosphorus in size fractions of sandy soils with different fertilization histories

A major challenge in sustainable crop management is to ensure adequate P supply for crops, while minimizing losses of P that could negatively impact water quality. The objective of the present study was to investigate the effects of long‐term applications of different levels of mineral fertilizers and farmyard manure on (1) the availability of P, (2) the relationship between soil C, N, and P, and (3) the distribution of inorganic and organic P in size fractions obtained by wet sieving. Soil samples were taken from the top 20 cm of a long‐term (29 y) fertilization trial on a sandy Cambisol near Darmstadt, SW Germany. Plant‐available P, determined with the CAL method, was little affected by fertilization treatment (p < 0.05) and was low to optimal. The concentration of inorganic and organic P extracted with a NaOH‐EDTA solution (P_NaOH‐EDTA) averaged about 350 mg (kg dry soil)^–1, with 42% being in the organic form (P_o). Manure application tended to increase soil C, N, and P_o concentrations by 8%, 9%, and 5.6%, respectively. Across all treatments, the C : N : P_o ratio was 100 : 9.5 : 2 and was not significantly affected by the fertilization treatments. Aggregate formation was weak due to the low clay and organic‐matter content of the soil, and the fractions > 53 μm consisted predominantly of sand grains. The different fertilization treatments had little effect on the distribution of size fractions and their C, N, and P contents. In the fractions > 53 μm, P_NaOH‐EDTA ranged between 200 and 300 mg kg^–1, while it reached 1260 mg kg^–1 in the fraction < 53 μm. Less than one third of P_NaOH‐EDTA was present as P_o in the fractions > 53 μm, while P_o accounted for 70% of P_NaOH‐EDTA in the smallest fraction (< 53 μm). Therefore, 16% and 28% of P_NaOH‐EDTA and P_o, respectively, were associated with the smallest fraction, even though this fraction accounted for < 5% of the soil mass. Therefore, runoff may cause higher P losses than the soil P content suggests in this sandy soil with a weak aggregate formation. Overall, the results indicate that manure and mineral fertilizer had similar effects on soil P fractions.     

Soil phosphorus fractions after seven decades of fertilizer application in the Rengen Grassland Experiment

Declining global P reserves require a better understanding of P cycling in soil and related plant uptake. On managed grasslands, application of lime and fertilizer affects not only soil nutrient status, but also plant‐species composition of the sward. We examined the P fractionation in the Rengen Grassland Experiment (RGE) on a naturally acid Stagnic Cambisol in the Eifel Mts. (Germany) 69 y after the setup of the experiment. A modified sequential Hedley fractionation was carried out for samples from 30 plots at 0–10 cm depth. Application of inorganic phosphorus fertilizer had diverse effects on inorganic (P_i) and organic P (P_o) fractions. Resin‐P_i, NaHCO₃‐P_i, NaHCO₃‐P_o, NaOH‐P_i, HCl_dil‐P_i, HCl_conc‐P_i, and HCl_conc‐P_o contents increased, while NaOH‐P_o significantly decreased and residual‐P remained unaffected. Strongest enrichment occurred in the HCl_dil‐P_i fraction, probably due to the chemical nature of the basic Thomas slag applied as P fertilizer. Without P fertilization, all fractions except residual‐P were more or less depleted. Strong P limitation of the vegetation in the limed treatments without P led to lowered contents also for NaOH‐P_i and NaOH‐P_o. However, NaOH‐P_o was largest in the Control and even exceeded the respective content in the treatments with P. It remained unclear why species adapted to a low soil P status did not access this P fraction though being P‐limited. Published theory on the availability of Hedley P fractions does neither match P exploitation nor P nutritional status of the vegetation in the RGE. Regarding NaOH‐P_o as stable and HCl_dil‐P_i as moderately labile led to a more realistic evaluation of plant P uptake. Evaluation of P availability on the basis of chemical extractions alone is questionable for conditions like in the RGE. On long‐term grassland, plant‐species composition has to be taken into account to estimate access of plants to soil P.     

Organic and Inorganic Forms of Phosphorus in a Calcareous Soil Planted with Four Species of Eucalyptus in Southern Iran

The objectives of the present study were to evaluate the effect of four eucalyptus species on (i) selected surface soil properties and (ii) the distribution of inorganic and organic phosphorus (P_i and P_o) fractions. Soil samples were collected from soil 0–20 cm deep beneath and between trees. The P_i forms were determined by sequential extraction with sodium bicarbonate (NaHCO₃‐P), ammonium acetate (NH₄OAc) (OAc‐P), ammonium fluoride (NH₄F‐P), sodium hydroxide (NaOH)–sodium carbonate (Na₂CO₃) (HC‐P), citrate dithionite (CD‐P), and sulfuric acid (H₂SO₄) (H₂SO₄‐P). The P_o forms were sequentially extracted with NaHCO₃ (NaHCO₃‐P_o), NaOH (NaOH‐P_o), and H₂SO₄ (H₂SO4‐P_o). The NaOH‐P_o was subdivided into moderately stable (NaOH‐P_om) and highly stable P_o (NaOH‐P_os). Organic matter, clay and silt contents, total nitrogen, and available potassium of the soil beneath the trees increased. The OAc‐P and HC‐P forms beneath the trees were less than of that between them, which shows that these fractions probably are labile inorganic P pools. The NaHCO₃‐P_o and NaOH‐P_os forms were greater beneath the trees than those of interspaces, whereas NaOH‐P_om and H₂SO₄‐P_o were not affected by plantation.