XANES spectroscopic analysis of phosphorus speciation in alum-amended poultry litter

Aluminum sulfate (alum; Al(2)(SO(4))(3).14H(2)O) is used as a chemical treatment of poultry litter to reduce the solubility and release of phosphate, thereby minimizing the impacts on adjacent aquatic ecosystems when poultry litter is land applied as a crop fertilizer. The objective of this study was to determine, through the use of X-ray absorption near edge structure (XANES) spectroscopy and sequential extraction, how alum amendments alter P distribution and solid-state speciation within the poultry litter system. Our results indicate that traditional sequential fractionation procedures may not account for variability in P speciation in heterogeneous animal manures. Analysis shows that NaOH-extracted P in alum amended litters is predominantly organic ( approximately 80%), whereas in the control samples, >60% of NaOH-extracted P was inorganic P. Linear least squares fitting (LLSF) analysis of spectra collected of sequentially extracted litters showed that the P is present in inorganic (P sorbed on Al oxides, calcium phosphates) and organic forms (phytic acid, polyphosphates, and monoesters) in alum- and non-alum-amended poultry litter. When determining land application rates of poultry litter, all of these compounds must be considered, especially organic P. Results of the sequential extractions in conjunction with LLSF suggest that no P species is completely removed by a single extractant. Rather, there is a continuum of removal as extractant strength increases. Overall, alum-amended litters exhibited higher proportions of Al-bound P species and phytic acid, whereas untreated samples contained Ca-P minerals and organic P compounds. This study provides in situ information about P speciation in the poultry litter solid and about P availability in alum- and non-alum-treated poultry litter that will dictate P losses to ground and surface water systems.     

Determination of phosphorus speciation in dairy manure using XRD and XANES spectroscopy

Intensive manure application is an important source of diffuse phosphorus (P) pollution. Phosphorus availability from animal manure is influenced by its chemical speciation. The major objective of this study was to investigate the P speciation in raw and anaerobically digested dairy manure with an emphasis on the calcium (Ca) and magnesium (Mg) phosphate phases. Influent and effluent from an on-farm digester in Wisconsin were sampled and sieved, and the 25 to 53 microm size fraction was dried for X-ray powder diffraction (XRD) and P K-edge X-ray absorption near edge structure (XANES) analyses. Struvite (MgNH4PO4.6H2O) was identified in both the raw (influent) and anaerobically digested (effluent) manure using XRD. Qualitative analysis of P K-edge XANES spectra indicated that the Ca orthophosphate phases, except dicalcium phosphate anhydrous (DCPA) or monetite (CaHPO4), were not abundant in dairy manure. Linear combination fitting (LCF) of the P standard compounds showed that 57.0 and 43.0% of P was associated with DCPA and struvite, respectively, in the raw manure. In the anaerobically digested sample, 78.2% of P was present as struvite and 21.8% of P was associated with hydroxylapatite (HAp). The P speciation shifted toward Mg orthophosphates and least soluble Ca orthophosphates following anaerobic digestion. Similarity between the aqueous orthophosphate (aq-PO4), newberyite (MgHPO4.3H2O), and struvite spectra can cause inaccurate P speciation determination when dairy manure is analyzed solely using P K-edge XANES spectroscopy; however, XANES can be used in conjunction with XRD to quantify the distribution of inorganic P species in animal manure.     

A comparison of phosphorus speciation and potential bioavailability in feed and feces of different dairy herds using 31p nuclear magnetic resonance spectroscopy

An experiment was conducted to examine how potential phosphorus (P) bioavailability (inferred from speciation) differs in feed and feces collected in spring from four dairy herds representing different management systems: (i) total confinement with cows fed total mixed ration (TMR), (ii) total confinement with TMR plus P mineral supplement, (iii) a hybrid of confinement with TMR and pastoral grazing, and (iv) predominantly grazing with supplemental grains. A treatment was included that air dried feces to simulate conditions after dung deposition. Wet chemical techniques and solution (31)P nuclear magnetic resonance spectroscopy ((31)P-NMR) were used to identify P concentrations and compounds present in water (a surrogate for P in overland flow), dilute acid (0.012 M HCl, an estimate of P utilization by cattle), or NaOH-EDTA (a solution that maximizes the organic P extraction) extracts of feed and feces. In general, P concentration in feces paralleled P in feed. Air drying feces decreased water-extractable P by 13 to 61% largely due to a decrease in orthophosphate, whereas NaOH-EDTA-extractable P increased by 18 to 48%. Analysis of dilute HCl was unsuccessful due to orthophosphate precipitation when pH was adjusted to 12 for (31)P-NMR. In water extracts, more P was in bioavailable diester-P forms, undetectable by colorimetry, than in NaOH-EDTA extracts. In feed, orthophosphate dominated (46-70%), but myo-IHP varied with feed (<10% in forage samples but 43% in a TMR sample). The proportion of myo-IHP decreased in feces compared with feed via mineralization but decreased less in systems with a greater proportion of available P input (e.g., orthophosphate and phospholipids). Feed and drying effect the concentrations and forms of P in feces and their potential impact on soil and water quality. Although bioavailable P in feces from pasture-based and confined systems can be similar in spring, dung-P is distributed on a lower kg P ha(-1) rate in grazing systems. The best method to mitigate P loss from feces is to decrease P in feed.     

Phosphorus speciation in sequentially extracted agro-industrial by-products: evidence from X-ray absorption near edge structure spectroscopy

The phosphorus (P) in agro-industrial by-products--a potential source of freshwater eutrophication but also a valuable fertilizer--needs to be speciated to evaluate its fate in the environment. We investigated to what extent X-ray absorption near edge structure (XANES) spectroscopy at the P K- and L2.3-edges reflected differences in sequentially extracted filter cakes from sugarcane (Saccharum officinarum L.) (FIC) and niger seed (Guizotia abyssinica Cass.; NIC) processing industry in Ethiopia. The P fractionation removed more labile (54%) and H2SO4-P (28%) from FIC than from NIC (18% labile, 12% H2SO4-P). For the FIC residues after each extraction step, linear combination (LC) fitting of P K-edge spectra provided evidence for the enrichment of Ca-P after the NaOH-extraction and its almost complete removal after the H2SO4-treatment. The LC-fitting was unsuccessful for the NIC samples, likely because of the predominance of organic P compounds. The different proportions of Ca-P compounds between FIC (large) and NIC (small) were more distinctive in L2-than in the K-edge XANES spectra. In conclusion, the added value of complementary P K- and L2.3-edge XANES was clearly demonstrated, and the P fractionation and speciation results together justify using FIC and NIC as soil amendments in the tropics.     

Characterization of phosphorus species in biosolids and manures using XANES spectroscopy

Identification of the chemical P species in biosolids or manures will improve our understanding of the long-term potential for P loss when these materials are land applied. The objectives of this study were to determine the P species in dairy manures, poultry litters, and biosolids using X-ray absorption near-edge structure (XANES) spectroscopy and to determine if chemical fractionation techniques can provide useful information when interpreted based on the results of more definitive P speciation studies. Our XANES fitting results indicated that the predominant forms of P in organic P sources included hydroxylapatite, PO(4) sorbed to Al hydroxides, and phytic acid in lime-stabilized biosolids and manures; hydroxylapatite, PO(4) sorbed on ferrihydrite, and phytic acid in lime- and Fe-treated biosolids; and PO(4) sorbed on ferrihydrite, hydroxylapatite, beta-tricalcium phosphate (beta-TCP), and often PO(4) sorbed to Al hydroxides in Fe-treated and digested biosolids. Strong relationships existed between the proportions of XANES PO(4) sorbed to Al hydroxides and NH(4)Cl- + NH(4)F-extractable P, XANES PO(4) sorbed to ferrihydrite + phytic acid and NaOH-extractable P, and XANES hydroxylapatite + beta-TCP and dithionite-citrate-bicarbonate (DCB)- + H(2)SO(4)-extractable P (r(2) = 0.67 [P = 0.01], 0.78 [P = 0.01], and 0.89 [P = 0.001], respectively). Our XANES fitting results can be used to make predictions about long-term solubility of P when biosolids and manures are land applied. Fractionation techniques indicate that there are differences in the forms of P in these materials but should be interpreted based on P speciation data obtained using more advanced analytical tools.     

Wet chemical and phosphorus-31 nuclear magnetic resonance analysis of phosphorus speciation in a sandy soil receiving long-term fertilizer or animal manure applications

In areas under intensive livestock farming and with high application rates of animal manure, inorganic and organic phosphorus (P) may be leached from soils. Since the contribution of these P compounds to P leaching may differ, it is important to determine the speciation of P in these soils. We determined the effect of various fertilization regimes on the P speciation in NaOH-Na2EDTA (ethylenediaminetetraacetic acid) and water extracts of acidic sandy soil samples from the top 5 cm of grassland with wet chemical analysis and 31P nuclear magnetic resonance (NMR) spectroscopy. These soils had been treated for a period of 11 years with no fertilizer (control), N (no P application), N-P-K, or different animal manures. Inorganic P was highly elevated in the NaOH-Na2EDTA extracts of the soils amended with N-P-K or animal manures, while organic P increased only in the soil treated with pig slurry. Water-extractable P showed a similar trend. As indicated by 31P NMR, orthophosphate monoesters were the main organic P compounds in all soils. Our results suggest that long-term applications of large amounts of P fertilizer and animal manures caused an accumulation of inorganic P, resulting in an increase of the potential risk related to mobilization of inorganic P in the top 5 cm of these soils.     

Broiler diet modification and litter storage: impacts on phosphorus in litters, soils, and runoff

Modifying broiler diets to mitigate water quality concerns linked to excess phosphorus (P) in regions of intensive broiler production has recently increased. Our goals were to evaluate the effects of dietary modification, using phytase and reduced non-phytate phosphorus (NPP) supplementation, on P speciation in broiler litters, changes in litter P forms during long-term storage, and subsequent impacts of diets on P in runoff from litter-amended soils. Four diets containing two levels of NPP with and without phytase were fed to broilers in a three-flock floor pen study. After removal of the third flock, litters were stored for 440 d at their initial moisture content (MC; 24%) and at a MC of 40%. Litter P fractions and orthophosphate and phytate P concentrations were determined before and after storage. After storage, litters were incorporated with a sandy and silt loam and simulated rainfall was applied. Phytase and reduced dietary NPP significantly reduced litter total P. Reducing dietary NPP decreased water-extractable inorganic phosphorus (IP) and the addition of dietary phytase reduced NaOH- and HCl-extractable organic P in litter, which correlated well with orthophosphate and phytic acid measured by 31P nuclear magnetic resonance (NMR), respectively. Although dry storage caused little change in P speciation, wet storage increased concentrations of water-soluble IP, which increased reactive P in runoff from litter-amended soils. Therefore, diet modification with phytase and reduced NPP could be effective in reducing P additions on a watershed scale. Moreover, efforts to minimize litter MC during storage may reduce the potential for dissolved P losses in runoff.     

Phosphorus movement and speciation in a sandy soil profile after long-term animal manure applications

Long-term application of phosphorus (P) with animal manure in amounts exceeding removal with crops leads to buildup of P in soil and to increasing risk of P loss to surface water and eutrophication. In most manures, the majority of P is held within inorganic forms, but in soil leachates organic P forms often dominate. We investigated the mobility of both inorganic and organic P in profile samples from a noncalcareous sandy soil treated for 11 yr with excessive amounts of pig slurry, poultry manure, or poultry manure mixed with litter. Solution 31P nuclear magnetic resonance spectroscopy was used to characterize NaOH-EDTA-extractable forms of P, corresponding to 64 to 93% of the total P concentration in soil. Orthophosphate and orthophosphate monoesters were the main P forms detected in the NaOH-EDTA extracts. A strong accumulation of orthophosphate monoesters was found in the upper layers of the manure-treated soils. For orthophosphate, however, increased concentrations were found down to the 40- to 50-cm soil layers, indicating a strong downward movement of this P form. This was ascribed to the strong retention of orthophosphate monoesters by the solid phase of the soil, preventing orthophosphate sorption and facilitating downward movement of orthophosphate. Alternatively, mineralization of organic P in the upper layers of the manure-treated soils may have generated orthophosphate, which could have contributed to the downward movement of the latter. Leaching of inorganic P should thus be considered for the assessment and the future management of the long-term risk of P loss from soils receiving large amounts of manure.     

Speciation of phosphorus in phosphorus-enriched agricultural soils using X-ray absorption near-edge structure spectroscopy and chemical fractionation

Knowledge of phosphorus (P) species in P-rich soils is useful for assessing P mobility and potential transfer to ground water and surface waters. Soil P was studied using synchrotron X-ray absorption near-edge structure (XANES) spectroscopy (a nondestructive chemical-speciation technique) and sequential chemical fractionation. The objective was to determine the chemical speciation of P in long-term-fertilized, P-rich soils differing in pH, clay, and organic matter contents. Samples of three slightly acidic (pH 5.5-6.2) and two slightly alkaline (pH 7.4-7.6) soils were collected from A or B horizons in two distinct agrosystems in the province of Québec, Canada. The soils contained between 800 and 2100 mg total P kg(-1). Distinct XANES features for Ca-phosphate mineral standards and for standards of adsorbed phosphate made it possible to differentiate these forms of P in the soil samples. The XANES results indicated that phosphate adsorbed on Fe- or Al-oxide minerals was present in all soils, with a higher proportion in acidic than in slightly alkaline samples. Calcium phosphate also occurred in all soils, regardless of pH. In agreement with chemical fractionation results, XANES data showed that Ca-phosphates were the dominant P forms in one acidic (pH 5.5) and in the two slightly alkaline (pH 7.4-7.6) soil samples. X-ray absorption near-edge structure spectroscopy directly identified certain forms of soil P, while chemical fractionation provided indirect supporting data and gave insights on additional forms of P such as organic pools that were not accounted for by the XANES analyses.     

Comparison of phosphorus forms in wet and dried animal manures by solution phosphorus-31 nuclear magnetic resonance spectroscopy and enzymatic hydrolysis

Both enzymatic hydrolysis and solution (31)P nuclear magnetic resonance (NMR) spectroscopy have been used to characterize P compounds in animal manures. In this study, we comparatively investigated P forms in 0.25 M NaOH/0.05 M EDTA extracts of dairy and poultry manures by the two methods. For the dairy manure, enzymatic hydrolysis revealed that the majority of extracted P was inorganic P (56%), with 10% phytate-like P, 9% simple monoester P, 6% polynucleotide-like P, and 18% non-hydrolyzable P. Similar results were obtained by NMR spectroscopy, which showed that inorganic P was the major P fraction (64-73%), followed by 6% phytic acid, 14 to 22% other monoesters, and 7% phosphodiesters. In the poultry manure, enzymatic hydrolysis showed that inorganic P was the largest fraction (71%), followed by 15% phytate-like P and 1% other monoesters, and 3% polynucleotide-like P. NMR spectroscopy revealed that orthophosphate was 51 to 63% of extracted P, phytic acid 24 to 33%, other phosphomonoesters 6 to 12%, and phospholipids and DNA 2% each. Drying process increased orthophosphate (8.4% of total P) in dairy manure, but decreased orthophosphate (13.3% of total P) in poultry manure, suggesting that drying treatment caused the hydrolysis of some organic P to orthophosphate in dairy manure, but less recovery of orthophosphate in poultry manure. Comparison of these data indicates that the distribution patterns of major P forms in animal manure determined by the two methods were similar. Researchers can utilize the method that best fits their specific research goals or use both methods to obtain a full spectrum of manure P characterization.     

Potential adverse effects of applying phosphate amendments to immobilize soil contaminants

Seven-day batch equilibrium experiments were conducted to measure the efficacy of four phosphate amendments (trisodium trimetaphosphate [TP3], dodecasodium phytate [Na-IP6], precipitated calcium phytate [Ca-IP6], and hydroxyapatite [HA]) for immobilizing Ni and U in organic-rich sediment. Using the eight-step modified Miller's sequential extraction procedure and the USEPA's Toxicity Characteristic Leaching Procedure, the effect of these amendments on the distribution of Ni and U was assessed. Relative to unamended controls, equilibrium aqueous-phase U concentrations were lower following HA and Ca-IP6 additions but higher following TP3 and Na-IP6 amendments, whereas aqueous Ni concentrations were not decreased only in the Na-IP6 amended treatment relative to the control. The poor rates of contaminant immobilization following TP3 and Na-IP6 amendments correlate with the dispersion of organic matter and organo-mineral colloids, which probably contain sorbed U and Ni. While all amendments shifted the U distribution toward more recalcitrant soil fractions, Ni was redistributed to more labile soil fractions. This study cautions that the addition of orthophosphates and organophosphates as contaminant immobilizing amendments may in fact have adverse effects, especially in high-organic soils. Particular attention is warranted at sites with mixed contaminants with varying geochemical behaviors.     

Phosphorus in fresh and dry dung of grazing dairy cattle, deer, and sheep: sequential fraction and phosphorus-31 nuclear magnetic resonance analyses

Knowledge of phosphorus (P) fractions in dung of animals (dairy cattle, deer, sheep) grazing pasture is important for soil fertility and the potential for P transport in runoff and subsequent surface water quality deterioration. We used sequential fractionation and 31P nuclear magnetic resonance (NMR) spectroscopy to determine P forms in fresh and air-dried (to simulate field conditions during grazing) dung. Sheep dung was richest in P (8 g kg(-1)), and cattle dung poorest (5.5 g kg(-1)). Data for sequential fractionation indicated that most P was extractable by water (15-36%) and bicarbonate (36-45%) in fresh dung, and shifted toward recalcitrant, HCl (12-28%), and residual P forms (15-31%) with drying. Organic P concentration in dung was poor (maximum of 15% of total P), probably due to the poor concentration of phytate in pasture. The 31P NMR spectra of NaOH-EDTA extracts supported this by detecting a low concentration of monoesters (9-19% of total P in extracts), of which phytate is a major component. The 31P NMR data also showed that changes in organic P concentration with drying could be due to the degradation of diesters. Data indicate the decreasing bioavailability of dairy cattle, deer, and sheep dung with drying and the need to consider this effect with respect to P returns for soil fertility and the potential for runoff.     

Influence of phytase addition to poultry diets on phosphorus forms and solubility in litters and amended soils

Diet modification to decrease phosphorus (P) concentration in animal feeds and manures can reduce surpluses of manure P in areas of intensive animal production. We generated turkey and broiler litters from two and three flock trials, respectively, using diets that ranged from "high" to "low" in non-phytate phosphorus (NPP) and some of which contained feed additives such as phytase. Phosphorus forms in selected litters were analyzed by sequential chemical fractionation and solution (31)P nuclear magnetic resonance (NMR) spectroscopy. Selected litters were also incubated with four contrasting soils. Reducing dietary NPP and using phytase decreased total P in litters by up to 38%. Water-soluble phosphorus (WSP) in litters was decreased 21 to 44% by feeding NPP closer to animal requirement, but was not affected by phytase addition. Solution (31)P NMR spectroscopy showed that feeding NPP closer to requirement decreased orthophosphate in litters by an average of 38% and that adding phytase to feed did not increase the concentration of orthophosphate in litters. Phytase also decreased phytate P in litters by 25 to 38%, demonstrating that it increases phytate P hydrolysis. Incorporation of litters with soils at the same total P rate increased WSP in soils relative to the control; this increase was correlated to soluble P added with litters at 5 d, but not by 29 d. Changes in soil Mehlich-3 phosphorus (M3-P) were related to total P added in litter, rather than soluble P. We conclude that feeding NPP closer to requirement and using feed additives such as phytase decrease total P concentrations in litters, while having little effect on P solubility in litters and amended soils.     

Phosphorus speciation in broiler litter and turkey manure produced from modified diets

Modifying poultry diets by reducing mineral P supplementation and/or adding phytase may change the chemical composition of P in manures and affect the mobility of P in manure-amended soils. We studied the speciation of P in manures produced by broiler chickens and turkeys from either normal diets, or diets with reduced amounts of non-phytate phosphorus (NPP) and/or phytase, using a combination of chemical fractionation and synchrotron X-ray absorption near edge structure (XANES) spectroscopy. All broiler litters were rich in dicalcium phosphate (65-76%), followed by aqueous phosphate (13-18%), and phytic acid (7-20%); however, no hydroxylapatite was observed. Similarly, normal turkey manure had 77% of P as dicalcium phosphate and had no hydroxylapatite, while turkey manure from diets that had reduced NPP and phytase contained equal proportions of dicalcium phosphate (33-45%) and hydroxylapatite (35-39%). This is attributed to the higher total Ca to P ratio (>2) in modified turkey manures that resulted in transformation of more soluble (dicalcium phosphate) to less soluble P compounds (hydroxylapatite). Chemical fractionation showed that H2O-extractable P was the predominant form in broiler litter (56-77%), whereas aqueous phosphate determined with XANES was <18% indicating that H2O probably dissolved mineral forms of P (e.g., dicalcium phosphate). Results show that HCl extraction primarily removed phytic acid from broiler litters and normal turkey manure, while it removed a mixture of hydroxylapatite and phytic acid from modified turkey manures. The combination of chemical fractionation and XANES provided information about the nature of P in these manures, which may help to devise best management practices for manure use.     

Effect of methodology in estimating and interpreting water-extractable phosphorus in animal manures

Manure water-extractable phosphorus (WEP) data are used in indices and models to assess P transport in runoff. Methods to measure WEP vary widely, often without understanding the effect on how much P is extracted. We conducted water extractions on five dairy, swine, and poultry manures to assess single and sequential extractions, drying manures, solution to solid (cm3 g(-1)) extraction ratios, and P determination method. We found little difference in WEP of single or sequential extractions. Increasing extraction ratio from 10:1 to 250:1 resulted in more WEP recovered, but in a diminishing fashion so that ratios of 200:1 and 250:1 were not significantly different. Patterns of increased WEP with extraction ratio varied with manure type, presence of bedding material, and drying treatment. Fresh and air-dried manures had similar patterns, but differed substantially from oven-dried (90 degrees C) manures. The differential effect of oven-drying on WEP was greatest for dairy and poultry manure, and less for swine manure. We analyzed water extracts colorimetrically before and after digestion, to examine the potential effect of P determination by inductively coupled plasma (ICP) spectroscopy. Digested extracts always contained more P. For manures with bedding, drying decreased the difference in P measured before and after digestion. The opposite was true for manures without bedding. Results highlight the influence of methodology on manure WEP measurement and caution needed when comparing data across studies using different WEP methods. Overall, our results point to a need for a standard manure water extraction method.     

Organic phosphorus fractions in organically amended paddy soils in continuously and intermittently flooded conditions

Soil organic phosphorus (SOP) can greatly contribute to plant-available P and P nutrition. The study was conducted to determine the effects of organic amendments on organic P fractions and microbiological activities in paddy soils. Samples were collected at the Changshu Agro-ecological Experiment Station in Tahu Lake Basin, China, from an experiment that has been performed from 1999 to 2004, on a paddy soil (Gleysols). Treatments consisted of swine manure (SM), wheat straw (WS), swine manure plus wheat straw (SM + WS), and a control (chemical fertilization alone). Organic amendments markedly increased soil total organic phosphorus (TOP) and total organic carbon (TOC), especially in continuously flooded conditions. Based on the fractionation of SOP, organic amendments significantly increased soil labile organic phosphorus (LOP), moderately labile organic phosphorus (MLOP), and moderately stable organic phosphorus (MSOP) compared with the control. For SM and SM + WS treatments, LOP in continuously flooded soils decreased by 30.1 and 36.4%, respectively, compared to intermittently flooded soils. In organically amended soils, continuous flooding showed significantly lower microbial biomass phosphorus (MBP) and alkaline phosphatase activities (APA) than intermittent flooding. In intermittently flooded conditions, incorporating organic amendments into soil resulted in greater P uptake and biomass yield of rice than the control. In the intermittently flooded soils, APA (P < 0.05) and MBP (P < 0.01) were significantly and positively related to TOP, LOP, MLOP, and MSOP, whereas in continuously flooded soils, there was a significant (P < 0.05) negative relationship between MBP, TOP, and MSOP. Based on soil organic P fractions and soil enzymatic and microbiological activities, continuous flooding applied to paddy soils should be avoided, especially when swine manure is incorporated into paddy soil.     

How accurate is the assessment of phosphorus pools in poultry litter by sequential extraction?

Amending poultry litter with Al sulfate (alum) has proven effective in reducing water-soluble P in the litter and in runoff from fields that have received litter applications. Although its effectiveness has been demonstrated on a macroscopic scale in the field or in the poultry houses, little is known about P speciation in either alum-amended or unamended litter. This knowledge is important for the evaluation of long-term stability and bioavailability of P, which is a necessary prerequisite for the assessment of the sustainability of intensive poultry operations. Here we report results from an investigation of alum-amended poultry litter (PL) that combined a chemical extraction sequence with solid-state 31P nuclear magnetic resonance (NMR) spectroscopic analysis of the residues. Aluminum is predominantly found in the fine size separate (<125 microm), indicating that the alum added to the poultry houses hydrolyzed without being completely dispersed in the litter. The NMR spectra confirmed the hypothesis that calcium phosphate phases are only dissolved during extraction with dilute acid and phosphate associated with Al is mainly dissolved during extraction with NaOH. Extraction of phosphate associated with Al was incomplete, however, as evidenced by 31P NMR spectroscopy. It could also be demonstrated that the extraction sequence overestimates the calcium phosphate fraction by an order of magnitude in this particular sample. Results from sequential chemical extraction should therefore be used with caution when assessing the magnitude of different phosphate pools in poultry litter.     

Optimizing phosphorus characterization in animal manures by solution phosphorus-31 nuclear magnetic resonance spectroscopy

A procedure involving alkaline extraction and solution 31P nuclear magnetic resonance (NMR) spectroscopy was developed and optimized for the characterization of P in animal manures (broiler, swine, beef cattle). Inclusion of ethylenediaminetetraacetic acid (EDTA) in the alkaline extraction solution recovered between 82 and 97% of the total P from the three manures, which represented a significant improvement on recovery in NaOH alone. Low concentrations of paramagnetic ions in all manure extracts meant that relatively long delay times (> 5 s) were required for quantitative analysis by solution 31P NMR spectroscopy. The manures contained inorganic orthophosphate, orthophosphate monoesters, orthophosphate diesters, and inorganic polyphosphates, but results were markedly influenced by the concentration of NaOH in the extractant, which affected both spectral resolution and the apparent P composition of the extracts. For example, extraction of swine manure and broiler litter with 0.5 M NaOH + 50 mM EDTA produced remarkable spectral resolution that allowed accurate quantification of the four signals from phytic acid, the major organic P compound in these manures. In contrast, more dilute NaOH concentrations produced considerable line broadening that obscured individual signals in the orthophosphate monoester region of the spectra. Spectral resolution of cattle manure extracts was relatively unaffected by NaOH concentration. Improvements in spectral resolution of more concentrated NaOH extracts were, however, compromised by the disappearance of phospholipids and inorganic polyphosphates, notably in swine and cattle manure extracts, which indicated either degradation or a change in solubility. The optimum extraction conditions will therefore vary depending on the manure type and the objectives of the study. Phytic acid can be accurately quantified in swine manure and broiler litter by extraction with 0.5 M NaOH + 50 mM EDTA, while a more dilute NaOH concentration should be used for complete P characterization or comparison among different manure types.     

Phosphorus runoff from incorporated and surface-applied liquid swine manure and phosphorus fertilizer

Excessive fertilization with organic and/or inorganic P amendments to cropland increases the potential risk of P loss to surface waters. The objective of this study was to evaluate the effects of soil test P level, source, and application method of P amendments on P in runoff following soybean [Glycine max (L.) Merr.]. The treatments consisted of two rates of swine (Sus scrofa domestica) liquid manure surface-applied and injected, 54 kg P ha(-1) triple superphosphate (TSP) surface-applied and incorporated, and a control with and without chisel-plowing. Rainfall simulations were conducted one month (1MO) and six months (6MO) after P amendment application for 2 yr. Soil injection of swine manure compared with surface application resulted in runoff P concentration decreases of 93, 82, and 94%, and P load decreases of 99, 94, and 99% for dissolved reactive phosphorus (DRP), total phosphorus (TP), and algal-available phosphorus (AAP), respectively. Incorporation of TSP also reduced P concentration in runoff significantly. Runoff P concentration and load from incorporated amendments did not differ from the control. Factors most strongly related to P in runoff from the incorporated treatments included Bray P1 soil extraction value for DRP concentration, and Bray P1 and sediment content in runoff for AAP and TP concentration and load. Injecting manure and chisel-plowing inorganic fertilizer reduced runoff P losses, decreased runoff volumes, and increased the time to runoff, thus minimizing the potential risk of surface water contamination. After incorporating the P amendments, controlling erosion is the main target to minimize TP losses from agricultural soils.     

Phosphorus speciation in manure-amended alkaline soils

Two common manure storage practices are stockpiles and lagoons. The manure from stockpiles is applied to soils in solid form, while lagoon manure is applied as a liquid. Soil amendment with manure in any form introduces a significant amount of phosphorus (P) that exists in both organic and inorganic forms. However, little is known about P speciation in manure stored under different conditions, or the subsequent forms when applied to soils. We used solution (31)P nuclear magnetic resonance (NMR) spectroscopy and conventional P fractionation and speciation methods to investigate P forms in dairy manure and liquid lagoon manure, and to study how long-term amendment with these manures influenced surface and subsurface soil P speciation. Our results show that the P forms in solid and lagoon manure are similar. About 30% of the total P was organic, mostly as orthophosphate monoesters. On a dry weight basis, total P was much higher in the solid manure. In the manure-amended soils the total P concentrations of the surface soils were similar, regardless of manure type. Total P in the subsurface soil was greater in the lagoon-manure-amended soil than the solid-manure-amended subsurface soil. However, the fraction of organic P was greater in the subsurface of the solid-manure-amended soil. The NMR results indicate that the majority of organic P in the soils is phytic acid, which is enriched in the surface soils compared with the subsurface soils. These results provide insight into P speciation and dynamics in manure-amended soils that will further increase our understanding on how best to manage manure disposal on soils.