Phosphorus status on Canadian organic farms

In eastern North America, many conventional livestock farms, especially dairy farms with high inputs of feed and fertiliser have excess soil phosphorus levels and an annual phosphorus surplus. However, a Canadian dairy farm in transition to organic, without fertiliser inputs reduced its farm P surplus to a marginal level. On long‐term organic dairy farms in Ontario, most soils tested low to very low in available P as measured by a standard soil test. Canadian Prairie organic grain farms also consistently demonstrate deficiencies in available soil P. Organic producers have few viable alternatives for P management. Phosphate rock can be acceptable to organic standards (provided they are low in heavy metals, and not processed synthetically), but the P in these becomes available slowly, especially in high pH soils common on most organic farms in Canada. An alternative is to increase soil P availability. Enhanced microbial activity in organically managed soils may make P more available. Livestock manures are rich sources of available phosphorus, but a majority of organic farmers in Canada do not keep livestock. Off‐farm manure sources are subject to organic regulations and hauling costs, both of which may be prohibitive. Furthermore, manure from conventional farms in Canada may be contaminated by genetically modified material from corn and soybean feed. Additional research is required to improve short‐term availability of soil P and long‐term replacement. Copyright © 2007 Society of Chemical Industry     

Correction for seed-phosphorus effects in L-value determinations

Measurements of the specific activity of plants grown in ³²P-labelled soils have frequently been used to estimate soil labile phosphorus (L-values). It is usually assumed that the plant-P uptake is totally derived from soil-P. The contribution of seed-P to plant-P uptake and L-values is seldom considered. This paper describes results of an experiment which measured the effects of seed-P on L-values and how correction for seed-P effects may be made when only the tops of plants are analysed. L-values were obtained from three harvests of ryegrass grown in three soils of very low, low and medium P status (soils I, II and III), containing 4, 14 and 37 mg initial NaHCO₃-soluble P kg^?1 soil, and supplied with increasing amounts of added P. Ryegrass, supplied with increasing amounts of ³²P-labelled ³¹P, was simultaneously grown in P-free sand, under identical experimental conditions to the soil-grown plants. The seed-P in the tops of the sand-grown plants, at increasing dry matter yields, was calculated and used to make appropriate corrections for seed-P in the tops of soil-grown plants. After correction for seed-P effects, L-values were reduced at the first harvest by 69% in soil I, 18% in soil II and 10% in soil III, at the second harvest by 27, 11 and 5%, and at the third harvest by 18, 6 and 4%, respectively. Increasing the amount of added P to soil-grown plants also caused some reduction in L-values in soil I but the effect was much less in soils II and III. The reduction in L-values at higher rates of added P in soil I was probably a result of increased P uptake diluting the effects of seed-P. In the other two soils, plant-P uptake was much greater, at all rates of added P, and this effect was very small.     

Evidence for bioavailable copper-dissolved organic matter complexes and transiently increased copper bioavailability in manure-amended soils as determined by bioluminescent bacterial biosensors

The short-term (3 months) dynamics of bioavailable copper (Cu) species was determined in soils amended with various amounts of manure and Cu. Bioavailable Cu species were operationally defined as those species that were able to induce gene expression in a Cu-specific Pseudomonas fluorescens biosensor. Biosensor measurements were backed by analysis of total Cu in soil and of total Cu and free Cu2+ ion activity in solution. Cu bioavailability relative to the total Cu concentration increased dramatically with increasing Cu loading of manure and with increasing manure amendment to soil. In both cases, the immediate increase in bioavailability could be explained in part by increased Cu concentration in solution and in part by an increased bioavailability of dissolved Cu species. In contrast to Cu bioavailability, Cu2+ ion activity decreased progressively with increasing manure loading. Cu bioavailability declined rapidly during the weeks after manure amendment concomitant with a marked slow-down of C mineralization indicating a shift from initially bioavailable Cu-dissolved organic matter (Cu-DOM) complexes to nonavailable Cu-DOM complexes over time. Our data do not support the conventional view of metal bioavailability being primarily related to the free metal ion activity and strongly suggest differential bioavailability of Cu-DOM complexes in manure-amended soils.     

Phosphorus speciation in manure and manure-amended soils using XANES spectroscopy

Previous studies suggested an increase in the proportion of calcium phosphates (CaP) of the total phosphorus (P) pool in soils with a long-term poultry manure application history versus those with no or limited application histories. To understand and predict long-term P accumulation and release dynamics in these highly amended soils, it is important to understand what specific P species are being formed. We assessed forms of CaP formed in poultry manure and originally acidic soil in response to different lengths of mostly poultry manure applications using P K-edge X-ray absorption near-edge structure (XANES) spectroscopy. Phosphorus K-edge XANES spectra of poultry manure showed no evidences of crystalline P minerals but dominance of soluble CaP species and free and weakly bound phosphates (aqueous phosphate and phosphate adsorbed on soil minerals). Phosphate in an unamended neighboring forest soil (pH 4.3) was mainly associated with iron (Fe) compounds such as strengite and Fe-oxides. Soils with a short-term manure history contained both Fe-associated phosphates and soluble CaP species such as dibasic calcium phosphate (DCP) and amorphous calcium phosphate (ACP). Long-term manure application resulted in a dominance of CaP forms confirming our earlier results obtained with sequential extractions, and a transformation from soluble to more stable CaP species such as beta-tricalcium calcium phosphate (TCP). Even after long-term manure application (> 25 yr and total P in soil up to 13,307 mg kg(-1)), however, none of the manure-amended soils showed the presence of crystalline CaP. With a reduction or elimination of poultry manure application to naturally acidic soils, the pH of the soil is likely to decrease, thereby increasing the solubility of Ca-bonded inorganic P minerals. Maintaining a high pH is therefore an important strategy to minimize P leaching in these soils.     

Long-term dynamics of phosphorus forms and retention in manure-amended soils

Phosphorus (P) leaching from soils with elevated P levels due to manure applications is increasingly becoming a concern as a source of eutrophication of streams and lakes. This study investigates the relationship between organic and inorganic P in soil pools and equilibrium leachate along a chronosequence of poultry and dairy manure additions in New York state. Resin-extractable P (molybdate-reactive P, RP) and total soil P reached very high levels of 2330 and 7343 mg of P kg(-1), respectively, after more than 25 years of continuous manure applications. After long-term manuring, the ability of these soils to retain additional P was low (Langmuir maximum sorption potential of 51-59 g of P kg(-1)) and equilibrium leachate concentrations of total dissolved P (TDP) were high (5.5-7.6 mg L(-1); saturated conditions, 0.15-m lysimeters in closed loop). Total dissolved P concentrations in equilibrium leachate increased linearly (r= 0.737) to a total soil P of 4500 mg kg(-1) and increased to a greater extent above 4500-5500 g kg(-1) (change point equivalent to about 1500 mg kg(-1) Mehlich 3-extractable RP). The proportion of dissolved unreactive P (DUP) in equilibrium leachate decreased from 90% of TDP in fields with a short manure application history to 2% of TDP where mainly poultry manure had been applied for >25 years, while unreactive P (UP) in soil decreased from 44% to 6%. Dissolved RP (DRP) was less mobile than DUP in soils with short duration of manure applications (p < 0.05), while differences between DUP and DRP mobility disappeared with longer duration of manure application and greater total soil P. Organic P forms in NaOH/NaF extracts determined by 31P NMR did not change with manure history, but sequential fractionation showed that the relative distribution of RP pools in soils changed. Dilute acid Pi increased from 10% to 62% with longer poultry manure additions, suggesting the formation of calcium phosphates as the soil pH increased from 4.1 to 6.0-7.2. The precipitation of P as calcium phosphates appeared to influence leachable P upon high and long-term applications of manure dominated by poultry litter.     

Phosphate uptake by lettuces and carrots from different soil depths in the field

In order to investigate the depths in field soils from which plants derive their phosphate nutrition, uptake of ³²P from depths of 6, 12, 24 and 36 inches was studied, using a shallow-rooted crop (lettuce) and a deeper-rooted crop (carrot). a soil at two different fertility levels was used, the higher level of fertility having been attained by heavy applications of farmyard manure over a period of twelve years. The exchangeable pool of phosphate in the high-fertility soil, at the depths investigated, was about twice that in the low-fertility soil. Total phosphate up take by lettuces on the two soils was almost proportional to the size of the exchangeable pool, but the uptake by carrots on the high-fertility soil was much less than twice that on the low-fertility soil. Phosphate uptake, computed as the product of measured radioactive phosphate and the size of the exchangeable phosphate pool at the depths investigated, shows that lettuces derived almost all their requirements of phosphate from the uppermost foot of soil. Carrots obtained most of their phosphate from this layer, but also obtained appreciable amounts from depths of 24 and 36 inches. Some implications of these findings are discussed.     

Differences in phosphorus and nitrogen delivery to the Gulf of Mexico from the Mississippi River Basin

Seasonal hypoxia in the northern Gulf of Mexico has been linked to increased nitrogen fluxes from the Mississippi and Atchafalaya River Basins, though recent evidence shows that phosphorus also influences productivity in the Gulf. We developed a spatially explicit and structurally detailed SPARROW water-quality model that reveals important differences in the sources and transport processes that control nitrogen (N) and phosphorus (P) delivery to the Gulf. Our model simulations indicate that agricultural sources in the watersheds contribute more than 70% of the delivered N and P. However, corn and soybean cultivation is the largest contributor of N (52%), followed by atmospheric deposition sources (16%); whereas P originates primarily from animal manure on pasture and rangelands (37%), followed by corn and soybeans (25%), other crops (18%), and urban sources (12%). The fraction of in-stream P and N load delivered to the Gulf increases with stream size, but reservoir trapping of P causes large local- and regional-scale differences in delivery. Our results indicate the diversity of management approaches required to achieve efficient control of nutrient loads to the Gulf. These include recognition of important differences in the agricultural sources of N and P, the role of atmospheric N, attention to P sources downstream from reservoirs, and better control of both N and P in close proximity to large rivers.     

Biogenic phosphate minerals in manure: implications for phosphorus loss to surface waters

Phosphorus (P) is present in waterways throughout the United States at concentrations that impair water quality. Agriculture, particularly livestock production, has been identified as a major cause of this impairment Excess manure P applied to croplands has increased P losses in runoff, leading to surface water eutrophication. We conducted a long-term (36-week) incubation with poultry and dairy manures applied to a silt loam soil to elucidate mechanisms controlling manure P loss to water. Manures were applied to supply the same total P rate to soils with different antecedent plant-available P concentrations (soil test P). There was a strong synergistic effect between dairy manure and soil test P on water extractable P, while soil test P did not affect P loss from poultry manure-amended soils. Using scanning electron microscopy and energy dispersive X-ray spectroscopy, we found that poultry manure contained sparingly soluble calcium and magnesium phosphate minerals that controlled soil solution P concentrations, while dairy manure did not These minerals resemble other biogenic phosphate minerals. Our findings refute current assumptions that all manure P behaves similarly in soils and that organic forms control manure-soil P loss to water.     

Interactions between soil and fertiliser in the supply of nitrogen to ryegrass grown on 21 soils

Perennial ryegrass (Lolium perenne L.) was grown in pots on 21 UK soils, both with and without fertiliser N. The fertiliser N was applied in six equal applications of ¹⁵N-labelled ammonium nitrate, each at the rate of 120 mg N per pot. The first application was mixed thoroughly with the soil, while subsequent applications were made in solution to the soil surface, after each of the first five of the six harvests of herbage. In the absence of fertiliser N, the proportion of the total soil N taken up by the plants, including stubble and roots at the sixth harvest, varied between 1.5 and 4.0%. In the presence of fertiliser N, the proportion varied between 2.1 and 4.7%. The apparent recovery of the fertiliser N was calculated from the difference between the amounts of N in the plants that received fertiliser N and in those that did not, expressed as a percentage of the amount applied. The actual recovery of the applied fertiliser N was determined by analysis of the plant material for ¹⁵N. With all soils at the first harvest, the apparent recovery was greater than the actual recovery. When calculated over all six harvests, apparent recovery of the total amount of fertiliser N was generally close to the actual recovery. This difference from the first harvest probably reflected (i) a reduction in the extent of turnover between fertiliser N and soil N when the fertiliser N was applied to the surface and (ii) a virtually complete uptake of available soil N by the end of the experiment, in both the absence and presence of fertiliser N. Differences between the 21 soils in actual recovery were not closely related, either positively or negatively, to a range of measured soil properties. A mean of 17.2% of the labelled fertiliser N was retained in the soil (excluding visible roots) at the end of the experiment. The lowest retention (6.2%) occurred with the soil which had the lowest contents of organic matter and silt plus clay but, with the other soils, the extent of retention varied only between 14.7 and 22.0% of that applied, and was not closely related to contents of total organic matter or macro-organic matter, or to the C:N ratio of the whole soil or the macro-organic matter.     

Phosphorus compounds in sequential extracts of animal manures: chemical speciation and a novel fractionation procedure

Pollution of water bodies by phosphorus in runoff from soil amended with animal manures is one of the greatest threats to water quality in developed countries. The environmental fate of manure phosphorus is determined in part by its chemical composition, yet extraction procedures to assess this are poorly developed and provide no structural information. We used solution 31P NMR spectroscopy to quantify phosphorus compounds in sequential extracts of three contrasting manures (broiler litter, beef-cattle manure, swine manure). Using a procedure originally developed for soils, but commonly applied to manures, phosphorus was extracted sequentially with deionized water, 0.5 M NaHCO3, 0.1 M NaOH, and 0.5 M HCl. Water and NaHCO3 extracted readily soluble compounds, including phosphate, phospholipids, DNA, and simple phosphate monoesters, which are mobile in soil and biologically available. In contrast, NaOH and HCl extracted poorly soluble compounds, including phytic acid (myoinositol hexakisphosphate). The latter is immobile in soil and of limited biological availability. Based on these results, we developed a simplified two-step fractionation procedure involving extraction of readily soluble phosphorus in 0.5 M NaHCO3 followed by extraction of stable phosphorus in a solution containing 0.5 M NaOH and 50 mM EDTA. This revised procedure separates manure phosphorus into structurally defined fractions with environmental relevance and will facilitate research on this important aspect of environmental science.     

The cation exchange properties and microbial carbon,nitrogen and phosphorus in savanna Alfisol under continuous cultivation

The study reports on the impact of inorganic fertilisers with or without farmyard manure on the cation exchange capacity (CEC), cationic balance and microbial biomass carbon (C), nitrogen (N) and phosphorus (P) in a savanna Alfisol after 45 years of cultivation. Soils for the study were fertilised with N or N+P+K, cow dung (D), D+N and D+N+P+K for 45 years. Inorganic fertiliser significantly reduced CEC, exchangeable cations and upset the cationic balance. The reduction in CEC and exchangeable cations seemed to operate via organic matter depletion and pH reduction. Similarly inorganic fertiliser stressed microbial activity evidenced by the low amounts of microbial biomass C, N and P compared to the soil under native vegetation and the soils fertilised with D+N and D+N+P+K. From the perspective of the flows of C, N and P through soil microbial biomass, and cation exchange properties and prevention of nutritional imbalances involving basic cations, a rational fertilisation program for savanna Alfisols is one that combines inorganic fertilisers with farmyard manures. ©1997 SCI     

Availability of Cu,Zn and Mn in soils: I.—Influence of soil pH,organic matter,and extractable phosphorus

Samples from Ap horizons of 36 cultivated Wisconsin fields were tested for concurrent availability of Cu, Zn and Mn. The effects of soil pH, organic matter, and available P were evaluated by using four chemical extract ants. Oats were used as the test crop and were grown using a self-watering pot-culture technique in a plant-growth room. The divergent soils had the following averages: pH, 6–4; organic matter, 2–6%; available P, 37 ppm; total Cu, 20 ppm; total Zn, 35 ppm; and total Mn, 631 ppm. Concentrations of the micronutrient elements in plants and soils were determined by atomic absorption spectrophotometer. NPK fertilisation resulted in greater plant uptake of Cu, Zn and Mn. Significant interactions between the soil properties and the different chemical fractions influenced the plant uptake of each micro-element; interactions between Cu, Zn and Mn in the same chemical fraction also influenced their individual uptake. Copper uptake was best predicted by inclusion particularly of soil pH, or the same chemical fractions of Zn and Mn in the regression equation; Zn uptake by inclusion of soil organic matter and available P, Mn uptake, or the chemical fractions of Cu and Mn; and Mn uptake by inclusion of available P, Cu chemical fraction, or Zn uptake in the equation. The extractants N ammonium acetate (pH 7) 10 · 01 M EDTA and 0·1 N -HCI show promise in soil tests for the simultaneous availability of Cu, Zn and Mn.     

Determination of phosphorus status of wheat and barley crops using a rapid root bioassay

A root bioassay of soil P availability, based on the amount of ³²P-labelled phosphorus taken up in 15 min from a solution in the laboratory, has been tested on seedlings of winter wheat (Triticum aestivum L) and spring barley (Hordeum vulgare L). The seedlings were taken in spring from six different fertiliser plots, selected to give an extreme range of P availability, from the Broadbalk and Hoosfield experiments at Rothamsted. The results showed a negative relationship between the rate of phosphorus uptake and (a) the phosphorus contents of plants, and (b) Olsen's bicarbonate extractable phosphorus of the soils. This pattern is consistent with the results previously obtained when determining the phosphorus status of trees and grasses. This rapid bioassay procedure may therefore be applicable to agricultural crops.     

The suitability of different methods for assessing the phosphorus status of hill soils

The availability of P for pasture plants in a range of acid hill soils with organic matter content up to 80% was assessed by extraction, exchange, sorption, isotopic dilution and digestion methods and was verified by plant P uptake using ryegrass and white clover as test plants. Values obtained by the conventional extraction and equilibration methods were inversely but non-significantly related to P uptake expressed in mg kg^?1 units: the relationships were only marginally improved with the data in mg litre^?1 units. The size of labile pool (‘L’ value) and amounts of both total- and organic-P ranked the soils in the same order as P uptake, but only when the data were expressed in mg litre^?1 units were the relationships highly significant. Reasons are suggested for the unsuitability of conventional extraction methods for acid, organic hill soils. Organic-P (in mg litre^?1 units) may provide the best indication of soil P status, but the determination of total-P appears to be the most practical alternative.     

Managing manure nutrients through multi-crop forage production

Concentrated sources of dairy manure represent significant water pollution potential. The southern United States may be more vulnerable to water quality problems than some other regions because of climate, typical farm size, and cropping practices. Dairy manure can be an effective source of plant nutrients and large quantities of nutrients can be recycled through forage production, especially when multi-cropping systems are utilized. Linking forage production with manure utilization is an environmentally sound approach for addressing both of these problems. Review of two triple-crop systems revealed greater N and P recoveries for a corn silage-bermudagrass hay-rye haylage system, whereas forage yields and quality were greater for a corn silage-corn silage-rye haylage system, when manure was applied at rates to supply N. Nutrient uptake was lower than application during the autumn-winter period, and bermudagrass utilized more of the remaining excess than a second crop of corn silage. Economic comparison of these systems suggests that the added value of the two corn silage crop system was not enough to off-set its increased production cost. Therefore, the system that included bermudagrass demonstrated both environmental and economic advantages. Review of the N and P uptake and calculated crop value of various single, double, and triple crop forage systems indicated that the per hectare economic value as well as the N and P uptakes tended to follow DM yields, and grasses tended to out-perform broadleaf forages. Taken across all systems, systems that included bermudagrass tended to have some of the highest economic values and uptakes of N and P. Manure applied at rates to supply N results in application of excess P, and production will not supply adequate quantities of forage to meet the herd's needs. Systems that lower manure application and supply supplemental N to produce all necessary forage under manure application will likely be less economically attractive due to additional costs of moving manure further and, applying it to greater land areas, but will be environmentally necessary in most cases. Intensive forage systems can produce acceptable to high quality forage, protect the environment, and be economically attractive. The optimal manure-forage system will depend on the farm characteristics and specific local conditions. Buffers and nutrient sinks can protect streams and water bodies from migrating nutrients and should be included as a part of crop production systems.     

Soil nitrate leaching under grazed cool-season grass pastures of the North Central US

Nitrate leaching from agricultural cropping systems contributes to widespread and devastating eutrophication of water bodies globally. In the North Central USA, this problem is acute, with millions of dollars spent annually in efforts to clean up recreational and drinking water. The frequent soil disturbance and exogenous nitrogen (N) amendments applied in annual cropping systems make them major sources of ground- and surface-water nitrate pollution. Perennial grasslands under managed livestock grazing have been touted for their ability to retain soils and nutrients while simultaneously providing milk and meat to society. The present study provides an evaluation of the peer-reviewed literature addressing nitrate leaching loads beneath corn, pasture and prairie in temperate humid and sub-humid regions of the US, with a focus on cool-season grass pastures. Inputs of exogenous N to these agroecosystems comes from wet and dry deposition, livestock manure from imported feed, biological fixation and inorganic N fertilizer. Nitrate loads were highest beneath corn and lowest beneath restored prairie and switchgrass managed for bioenergy. Cool-season grass pastures had relatively low levels of nitrate leaching loads where little or no N was applied. However, where grazed perennial grasslands had inorganic N applied, nitrate leaching loads rivaled those of corn in some cases. When producing milk and meat from livestock, grazed perennial cool-season grass pastures should reduce nitrate leaching loads compared to growing corn that is used to feed livestock in confinement. However, cool-season grass pastures can lose significant nitrate to leaching with moderate- to high-levels of exogenous N inputs. © 2020 Society of Chemical Industry     

The effect of soil Ph on olsen bicarbonate phosphate values

The effect of increases in soil pH by liming on Olsen bicarbonate phosphate (P) test values was investigated using two contrasting New Zealand soils: a highly P retentive Egmont soil and a Tokomaru soil with a low P retention capacity. After incubation with three rates of Ca(OH)₂, soil pH was increased, and a reduction in the Olsen P values was observed. The amounts of ³²P-exchangeable P, however, increased with increasing soil pH, and there was very little change in water-extractable P. The addition of lime had no significant effect on either the yield or uptake of P by ryegrass grown on the same soils in the glasshouse. It appears that the decline in Olsen P values in soils following liming is a result of an artefact in the Olsen procedure. High concentrations of Ca are involved in the decrease in Olsen P values in limed soils. It is suggested that the precipitation of calcium phosphates in the Olsen extracts of limed soils is responsible for the decrease in the Olsen P values. In a field experiment, increasing soil pH by lime addition also resulted in a decrease in the Olsen P values.     

Soil phosphate stable oxygen isotopes across rainfall and bedrock gradients

The stable oxygen isotope compositions of soil phosphate (δ(18)O(p)) were suggested recently to be a tracer of phosphorus cycling in soils and plants. Here we present a survey of bioavailable (resin-extractable or resin-P) inorganic phosphate δ(18)O(p) across natural and experimental rainfall gradients, and across soil formed on sedimentary and igneous bedrock. In addition, we analyzed the soil HCl-extractable inorganic δ(18)O(p), which mainly represents calcium-bound inorganic phosphate. The resin-P values were in the range 14.5-21.2‰. A similar range, 15.6-21.3‰, was found for the HCl-extractable inorganic δ(18)O(p), with the exception of samples from a soil of igneous origin that show lower values, 8.2-10.9‰, which indicate that a large fraction of the inorganic phosphate in this soil is still in the form of a primary mineral. The available-P δ(18)O(p) values are considerably higher than the values we calculated for extracellular hydrolysis of organic phosphate, based on the known fractionation from lab experiments. However, these values are close to the values expected for enzymatic-mediated phosphate equilibration with soil-water. The possible processes that can explain this observation are (1) extracellular equilibration of the inorganic phosphate in the soil; (2) fractionations in the soil are different than the ones measured at the lab; (3) effect of fractionation during uptake; and (4) a flux of intercellular-equilibrated inorganic phosphate from the soil microbiota, which is considerably larger than the flux of hydrolyzed organic-P.     

Linking phosphorus sequestration to carbon humification in wetland soils by 31P and 13C NMR spectroscopy

Phosphorus sequestration in wetland soils is a prerequisite for long-term maintenance of water quality in downstream aquatic systems, but can be compromised if phosphorus is released following changes in nutrient status or hydrological regimen. The association of phosphorus with relatively refractory natural organic matter (e.g., humic substances) might protect soil phosphorus from such changes. Here we used hydrofluoric acid (HF) pretreatment to remove phosphorus associated with metals or anionic sorption sites, allowing us to isolate a pool of phosphorus associated with the soil organic fraction. Solution (31)P and solid state (13)C NMR spectra for wetland soils were acquired before and after hydrofluoric acid pretreatment to assess quantitatively and qualitatively the changes in phosphorus and carbon functional groups. Organic phosphorus was largely unaffected by HF treatment in soils dominated by refractory alkyl and aromatic carbon groups, indicating association of organic phosphorus with stable, humified soil organic matter. Conversely, a considerable decrease in organic phosphorus following HF pretreatment was detected in soils where O-alkyl groups represented the major fraction of the soil carbon. These correlations suggest that HF treatment can be used as a method to distinguish phosphorus fractions that are bound to the inorganic soil components from those fractions that are stabilized by incorporation into soil organic matter.     

High-resolution characterization of organic phosphorus in soil extracts using 2D 1H-31P NMR correlation spectroscopy

Organic phosphorus (P) compounds represent a major component of soil P in many soils and are key sources of P for microbes and plants. Solution NMR (nuclear magnetic resonance spectroscopy) is a powerful technique for characterizing organic P species. However, (31)P NMR spectra are often complicated by overlapping peaks, which hampers identification and quantification of the numerous P species present in soils. Overlap is often exacerbated by the presence of paramagnetic metal ions, even if they are in complexes with EDTA following NaOH/EDTA extraction. By removing paramagnetic impurities using a new precipitation protocol, we achieved a dramatic improvement in spectral resolution. Furthermore, the obtained reduction in line widths enabled the use of multidimensional NMR methods to resolve overlapping (31)P signals. Using the new protocol on samples from two boreal humus soils with different Fe contents, 2D (1)H-(31)P correlation spectra allowed unambiguous identification of a large number of P species based on their (31)P and (1)H chemical shifts and their characteristic coupling patterns, which would not have been possible using previous protocols. This approach can be used to identify organic P species in samples from both terrestrial and aquatic environments increasing our understanding of organic P biogeochemistry.