Characterization of Soil Phosphorus in Differently Managed Clay Soil by Chemical Extraction Methods and 31P NMR Spectroscopy

Changes in land use alter the natural cycling of phosphorus (P) in soil. Understanding the chemical nature of these changes is important when developing sustainable management practices for cultivated soils. In this study, we evaluated the ability of commonly used laboratory methods to characterize land use–induced changes in various P pools. Also, the characteristics of soil P revealed by different methods are discussed. Soil samples were taken from three differently managed field plots of the same clay soil: uncultivated grassland and organic and conventional crop rotations. Soil P reserves were characterized using Chang and Jackson and Hedley sequential fractionation procedures and by sodium hydroxide (NaOH)–ethylenediaminetetraacetic acid (EDTA) extraction followed by ³¹P NMR spectroscopy. Both of the tested fractionation methods identified differences in the P pools and provided evidence regarding land use–induced changes. However, the ³¹P NMR analysis suggests that the quality of organic P in this soil was not affected by the change in land use.     

A combination method of hydrofluoric acid,oxalate and NaOH‐EDTA extractions to determine phosphorus species in soil by 31P‐NMR spectroscopy

The objective of this study was to investigate the applicability of selective extraction methods in combination with solution phosphorus‐31 (³¹P) nuclear magnetic resonance (NMR) for the determination of organic phosphorus (P_o) species in soil. Inositol hexakisphosphates (IHP) and glucose 6‐phosphate (GP) were identified in the soil. IHP adsorbed to both soil organic matter (SOM) and short‐range order (SRO) minerals, whereas GP adsorbed only to SOM. These results suggest that P_o hosting phases are different depending on P_o species.     

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.     

Characterization of Phosphorus in Sewage Sludge from Different Sources by 31Phosphorus Nuclear Magnetic Resonance Spectroscopy

To investigate the distribution and dynamics of phosphorus (P) in soils for environmental protection and agronomical usage, ³¹P nuclear magnetic resonance spectroscopy (³¹P NMR) was used to characterize the contents and chemical properties of P in sewage sludge from 13 wastewater treatment plants in Shanghai. The samples were extracted with 0.25 M sodium hydroxide (NaOH) / 0.05 M sodium ethylenediamietetraacetic acid (Na₂EDTA) in ratio of 1:20 (w/v). Total P recovery in the extract ranged from 91 to 116% when compared to traditional chemical methods. The dominant forms of P in all samples were inorganic orthophosphates and orthophosphates monoesters. Orthophosphate diesters and pyrophosphates were present in only two and four samples, respectively. This study provides detailed information on the distribution, contents, and chemical properties of P in sewage sludge that may be of value in the utilization of sewage sludge for agronomic purposes.     

Phosphorus Availability in Low-P and Acidic Soils as Affected by Liming and P Addition

Acidic soils typically suffer from high phosphorus (P) retention, a problem that can be dealt with using greater P fertilization, soil liming, or both. The aim of this work was to examine which of these practices bears the more beneficial result for Lolium perenne L. growth. In a pot experiment, five acidic soils were treated as follows: L0P0 (unamended control), L1P0 (liming only), L0P1 (P addition only), and L1P1 (both liming and P addition). We found that P amendment alone was sufficient to increase plant P levels when the initial soil P concentrations were low. Liming without P addition increased plant P satisfactorily only in the high-P soil. We conclude that P addition alone is a better practice than liming alone for improved plant growth conditions in acidic, low-P soils, unless there is relatively high P content in soil, in which case liming alone may be sufficient to increase P availability.     

Phosphorus fractions in poultry litter as affected by flue‐gas desulphurization gypsum and litter stacking

Previous research has shown that the addition of flue‐gas desulphurization (FGD) gypsum to poultry litter decreases water‐soluble P. No information is currently available, however, on extractable P fractions in poultry litter and P availability as affected by gypsum. The first objective of this work was to evaluate the effect of incubation time and rate of gypsum addition to litter alone or litter mixed with soil on total P and inorganic P in sequential extracts of H₂O, 0.5 m NaHCO₃, 0.1 m NaOH and 1 m HCl. Poultry litter was mixed with 25, 50, or 75% gypsum (by weight) and incubated alone or mixed with soil for 63–93 days at 25 °C, with periodic sequential extractions. For litter alone or litter mixed with soil, adding gypsum decreased total P and inorganic P in the H₂O fraction and increased both P forms in the NaHCO₃ fraction. These changes did not affect plant P availability as measured by Mehlich‐1 P. Increasing incubation time decreased total P and inorganic P in the H₂O fraction of litter alone or litter mixed with soil, which was apparently caused by P immobilization by fungi. A second objective of this study was to evaluate P in the H₂O and NaHCO₃ fractions of litter as affected by stacking time and depth. Litter was stacked to a height of 1.2 m with samples taken immediately after stacking and 31 days later to be sequentially extracted for total P and inorganic P. Stacking time did not affect P in the H₂O fraction, but it increased P in the NaHCO₃ fraction by 25%. These results suggest that stacking poultry litter may increase the amount of labile P.     

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.     

Comparison of Phosphorus Forms in Three Extracts of Dairy Feces by Solution 31P NMR Analysis

Using solution ³¹P NMR spectroscopy, we compared three extractants, deionized water, sodium acetate buffer (pH 5.0) with fresh sodium dithionite (NaAc-SD), and 0.25 M NaOH–0.05 M ethylenediaminetetraacetic acid (NaOH-EDTA), for the profile of P compounds in two dairy fecal samples. Phosphorus extracted was 35 percent for water and 80–100 percent for NaAc-SD and NaOH-EDTA. Water extracted a greater proportion of organic P forms, particularly orthophosphate diesters, but a lower proportion of orthophosphate relative to NaOH-EDTA and NaAc-SD. Phosphorus recoveries and spectra were generally similar for NaOH-EDTA and NaAc-SD, but there was increased degradation of polyphosphate to pyrophosphate with NaOH-EDTA, and water, for one sample relative to NaAc-SD. For studies characterizing and quantifying all the P forms in manure and fecal samples, these results suggest that either NaOH-EDTA or NaAc-SD would be a good choice. However, extraction with water may be a better choice for studies monitoring labile manure P and potential environmental impact.     

Recovery of phosphorus fertilizer in potato as affected by application strategy and soil type

Phosphorus (P) fertilizers are usually supplied prior to or at planting of potato even though most P is taken up 40 to 80 d after emergence. This may lead to inefficient P use as a result of P leaching or fixation in the soil. This study evaluates the effects of split P application at multiple times during the growth period according to the plant's need for P. Potato (Solanum tuberosum L. cv. Ditta) was grown in pots in climate chambers, and radioactive ³²P isotope was used to distinguish between the fertilizer and soil‐derived P sources. Two soils were tested in combination with five application rates of P, and the plants were harvested at four dates. The results show that the recovery of P fertilizer can be significantly enhanced if the P supply is split. The result also showed that the proportion of soil‐derived P, accumulated in the plant, was significantly reduced both when more fertilizer P was applied to the soil and when P supply was split into several applications. The positive effects of multiple P applications on the P recovery were greatest in the soil with low P status and low buffer capacity.     

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.     

Phosphorus acquisition and wheat growth are influenced by shoot phosphorus status and soil phosphorus distribution in a split‐root system

Root proliferation and greater uptake per unit of root in the nutrient‐rich zones are often considered to be compensatory responses. This study aimed to examine the influence of plant phosphorus (P) status and P distribution in the root zone on root P acquisition and root and shoot growth of wheat (Triticum aestivum L.) in a split‐root soil culture. One compartment (A) was supplied with either 4 or 14 mg P (kg soil)^–1, whereas the adjoining compartment (B) had 4 mg P kg^–1 with a vertical high‐P strip (44 mg kg^–1) at 90–110 mm from the plant. Three weeks after growing in the split‐root system, plants with 4 mg P kg^–1 (low‐P plants) started to show stimulatory root growth in the high‐P strip. Two weeks later, root dry weight and length density in the high‐P strip were significantly greater for the low‐P plants than for the plants with 14 mg P (kg soil)^–1. However, after 8 weeks of growth in the split‐root system, the two P treatments of compartment A had similar root growth in the high‐P strip of compartment B. The study also showed that shoot P concentrations in the low‐P plants were 0.6–0.8 mg g^–1 compared with 1.7–1.9 mg g^–1 in the 14 mg P kg^–1 plants after 3 and 5 weeks of growth, but were similar (1.1–1.4 mg g^–1) between the two plants by week 8. The low‐P plants had lower root P concentration in both compartments than those with 14 mg P kg^–1 throughout the three harvests. The findings may indicate that root proliferation and P acquisition under heterogeneous conditions are influenced by shoot P status (internal) and soil P distribution (external). There were no differences in the total root and shoot dry weight between the two P treatments at weeks 3 and 5 because enhanced root growth and P uptake in the high‐P strip by the low‐P plants were compensated by reduced root growth elsewhere. In contrast, total plant growth and total root and shoot P contents were greater in the 14 mg P kg^–1 soil than in the low‐P soil at week 8. The two P treatments did not affect the ratio of root to shoot dry weight with time. The results suggest that root proliferation and greater P uptake in the P‐enriched zone may meet the demand for P by P‐deficient plants only for a limited period of time.     

Content and composition of free and occluded particulate organic matter in a differently textured arable Cambisol as revealed by solid‐state 13C NMR spectroscopy

The composition of functional light soil organic matter pools of arable Cambisols with a gradient in clay content was investigated. Soil texture differences originate from increasing loess admixture to the parent material (coarse‐grained tertiary sediments). Using density fractionation in combination with ultrasonic dispersion, two types of particulate organic matter (POM) were obtained: (1) free POM and (2) POM occluded in soil aggregates. Both POM fractions were analyzed by elemental analysis (C, N) and CPMAS ¹³C NMR spectroscopy. With increasing clay content the amount of organic carbon stored in the occluded POM fraction increased considerably, whereas the amounts of free POM were not related to the soil clay content. With increasing soil clay contents increasing proportions of O‐alkyl C and decreasing proportions of aryl C were found for both POM fractions. The occluded POM fraction showed a higher degree of degradation as indicated by lower amounts in O‐alkyl carbon. A lower degree of POM degradation was associated with higher clay contents. Higher soil clay contents promoted the conservation of POM with a low degree of alteration. This effect of soil texture was found to be highly significant when the aryl C : O‐alkyl C ratio was used as indicator for POM decomposition rather than the alkyl C : O‐alkyl C ratio.     

Phosphorus compounds in subarctic Fennoscandian soils at the mountain birch (Betula pubescens)—tundra ecotone

Nutrient availability will partly regulate the response of high latitude ecosystems to climate warming, but phosphorus biogeochemistry is poorly understood in Arctic soils. We used NaOH-EDTA extraction and solution ³¹P nuclear magnetic resonance (NMR) spectroscopy to determine phosphorus compounds in subarctic soils from three locations in the Fennoscandian mountains contrasting in latitude and continentality. Soils were taken from open tundra and mountain birch (Betula pubescens Ehrh.) forest at each location. Between 87 and 95% of the total phosphorus was extracted from the surface 2 cm of the organic soil horizons. Most of the extracted phosphorus was orthophosphate monoesters (44-55%), with smaller concentrations of inorganic orthophosphate (15-24%), orthophosphate diesters (12-16%), pyrophosphate (3-18%), inorganic polyphosphate (0-15%) and phosphonates (0-4%). The orthophosphate diesters were further subclassified into DNA (9-13% extracted phosphorus) and phospholipids (1-6% extracted phosphorus), although strong signals in the orthophosphate monoester region of the spectra, consistent with the degradation of phosphatidyl choline in alkaline solution, suggested that phospholipid concentrations were substantially underestimated. The phosphorus composition was broadly similar among soils from the three locations, although no phosphonates were detected in tundra soils from the most southerly site. Deeper organic horizons tended to contain a greater proportion of orthophosphate monoesters than at the surface. The abundance of phosphorus compounds that would be considered readily degradable in temperate environments probably reflects the slow organic matter decomposition in these cold, acidic soils, and suggests that phosphorus availability is unlikely to limit ecosystem productivity on mesic soils at the birch-tundra ecotone during changes induced by climate warming.     

Phosphorus speciation and colloidal phosphorus responses to short-term cessation of fertilization in a lime concretion black soil

Long-term excessive application of mineral fertilizer has led to soil acidification and phosphorus(P) accumulation, increasing the risk of P loss and environmental pollution, and cessation of fertilization is widely considered as a cost-effective management strategy to relieve this situation; however, how such cessation influences P speciation and concentrations in a bulk soil and colloidal fractions and whether decreasing P concentration might maintain soil fertility remain unclear. In this stu...     

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.     

腐殖酸物质对磷在褐土中迁移的影响

采用室内土柱实验研究了腐殖酸和腐殖酸钠在与磷肥共施时对磷在褐土中迁移的影响。结果表明,与单施磷酸二氢钙相比,共施腐殖酸钠缩短了磷在土壤中的迁移距离,明显降低了施肥点附近微域中的水溶性磷和酸溶性磷含量,磷向土体中的迁移量也显著下降;相比之下,共施腐殖酸则明显增加了磷的迁移距离和迁移量,对肥际微域中不同形态磷的含量均有显著提高作用。因此,腐殖酸促进了磷在褐土中的迁移,适宜与磷肥配合施用,而腐殖酸钠不适合与磷肥共施。     

Phosphorus indices as risk‐assessment tools in the U.S.A. and Europe—a review

The “phosphorus index” (PI) is a semiquantitative tool to assess the risk of P loss from fields to surface waters, which is based on simple arithmetic computations of source (soil test phosphorus (STP), P applications as manure and fertilizer, plant residues) and transport factors (erosion, surface runoff, subsurface drainage, connectivity). Work done since the 1990s in the U.S.A. and several European countries has shown that this approach is capable of delineating critical source areas for P export within a watershed. It is intended to adopt such a PI tool in Germany as well. However, there is no “standard” PI, and the variety of P indices is confusing, since each state and country has developed its own version to account for special regional conditions which are important for P loss. This paper reviews the factors of P loss which are taken into account in P indices and different modifications of P indices according to their components and structural approach. The literature concerning single source and transport factors of P loss is overwhelming, and a structured selection is given in this review. Most P indices can be classed into one of three groups: 1. additive approach, 2. multiplicative approach, and 3. multiplicative‐additive approach. For Germany, it is suggested that specific factors of P loss are incorporated into the basic backbone of a Pennsylvania‐style PI. Realization of the factors could be adopted from existing Scandinavian P indices or from other research results.     

Analysis of phosphorus in two humic acid fractions of intensively cropped lowland rice soils by 31P‐NMR

The organic forms of phosphorus in the soil appear to be changing as rice growing intensifies and the soil is flooded for longer in tropical Asia. To examine these changes, we extracted the labile mobile humic acid (MHA) and more recalcitrant calcium humate (CaHA) fractions from soils supporting long‐term field trials in the Philippines and analysed them by solution ³¹P‐nuclear magnetic resonance (NMR) spectroscopy. Diester P and sugar‐diester P accumulated moderately with increasing intensity of irrigated rice cropping, reaching a combined 42% of all MHA‐P for a triple‐cropped irrigated field compared with 28% for fully aerated fields growing dryland crops. The mono‐ to diester P ratio decreased by 43% for the MHA and CaHA from the aerated fields to the triple‐cropped field. Smaller effects on forms of P were noted for the rates and type of N, P and K fertilizer and site effects. The effects of treatment and site were more noticeable in the MHA than in the CaHA. The proportions in the NMR spectra were tightly correlated with visible light absorption, concentrations of organic free radicals and H, and ¹⁵N‐NMR spectral proportions, which indicate the degree of humification. The MHA and CaHA accounted for only 0.6–8.3% and 0.9–5.7%, respectively, of total P; most of the P is inorganic.     

Phosphorus dynamics in peat‐based substrates

The mobility of nutrients in soils is well characterized, whereas little information is available for common horticultural substrates based on peat. Aim of the current study was to investigate the mobility and dynamics of phosphorus (P) as well as the parameters involved in P transport to plant roots in peat‐based substrates. A series of experiments was run to determine the impedance factor (f) and the buffer power (b). The impedance factor was determined for black peat and black peat mixed with 20% and 40% (v/v) of mineral component at volumetric water content (θ) of 40%, 50%, 60%, and 70% and at different diffusion time. Buffer power was calculated for black peat and black peat mixed with 20% (v/v) of seven different mineral components. Phosphorus was applied at rates of 0, 35, and 100 mg (L substrate^–1), respectively. The impedance factor was not affected by addition of the mineral component to peat. However, f increased from 0.03 to 0.2, by increasing θ from 40% to 60%, indicating that water content has a significant effect on this parameter. Substrate‐solution P ranged from 0.3 to 27 and from 1 to 95 mg P (L solution)^–1 for the P‐application rate of 35 and 100 mg P (L substrate)^–1, respectively. Buffer power of the substrates ranged from 1 to 17.25 depending on the mineral component, and it was positively correlated with oxalate‐soluble Fe and Al in the substrate. The calculated effective diffusion coefficient for P in the substrate was in the range of 10^–7 to 10^–8 cm² s^–1. This high value could be attributed mostly to the low buffer power rather than to the high impedance factor.