Enzymatic characterization of organic phosphorus in animal manure

Information on the forms of P present in animal manure may improve our ability to manage manure P. In most investigations of manure P composition, only inorganic and total P are determined, and the difference between them is assigned as organic P. In this study, we explored the possibility of identifying and quantifying more specific organic P forms in animal manure with orthophosphate-releasing enzymes. Pig (Sus scrofa) manure and cattle (Bos taurus) manure were first sequentially fractionated into water-soluble P, NaHCO3-soluble P, NaOH-soluble P, HCl-soluble P, and residual P. The fractions were separately incubated with wheat phytase, alkaline phosphatase, nuclease P1, nucleotide pyrophosphatase, or their combinations. The released orthophosphate was determined by a molybdate blue method. Part of the organic P in those fractions could be identified by the enzymatic treatments as phytate (i.e., 39% for pig manure and 17% for cattle manure in water-soluble organic P), simple phosphomonoesters (i.e., 43% for pig manure and 15% for cattle manure in NaOH-soluble organic P), nucleotide-like phosphodiesters (2-12%), and nucleotide pyrophosphate (0-4%). Our data indicate that the enzymatic treatment is an effective approach to identify and quantify the organic P forms present in animal manures.     

Phosphorus speciation of sequential extracts of organic amendments using nuclear magnetic resonance and X-ray absorption near-edge structure spectroscopies

The chemical forms of phosphorus in organic amendments are essential variables for proper management of these amendments for agro-environmental purposes. This study was performed to elucidate the forms of phosphorus in various organic amendments using state-of-the-art spectroscopic techniques. Anaerobically digested biosolids (BIO), hog (HOG), dairy (DAIRY), beef (BEEF), and poultry (POULTRY) manures were subjected to sequential extraction. The extracts and residues after extraction were analyzed by solution (31)P nuclear magnetic resonance (NMR) and synchrotron-based P 1s X-ray absorption near-edge structure (XANES) spectroscopies, respectively. Most of the total P analyzed by inductively coupled plasma- optical emission spectroscopy in the sequential extracts of organic amendments was orthophosphate, except POULTRY, which was dominated by organic P. The labile P fraction in all the organic amendments, excluding POULTRY, was mainly orthophosphate from readily soluble calcium and some aluminum phosphates. In the poultry litter, Ca phytate was the main P species controlling P solubility. The recalcitrant fraction of BIO was mainly associated with Al and Fe. Those of HOG, DAIRY, and POULTRY were calcium phytate, which were identified only as organic species in the XANES spectra. The combination of the three techniques-sequential chemical extraction, solution (31)P NMR spectroscopy, and P 1s XANES-provided molecular characterization of P in organic amendments that would not have been possible with just one or a combination of any two of these techniques. Therefore, P speciation of organic amendments should use solid-phase and aqueous speciation techniques as deemed feasible.     

Phosphorus distribution in dairy manures

The chemical composition of manure P is a key factor determining its potential bioavailability and susceptibility to runoff. The distribution of P forms in 13 dairy manures was investigated with sequential fractionation coupled with orthophosphate-releasing enzymatic hydrolysis. Among the 13 dairy manures, manure total P varied between 4100 and 18,300 mg kg(-1) dry matter (DM). Water-extractable P was the largest fraction, with inorganic phosphorus (P(i)) accounting for 12 to 44% of manure total P (1400-6800 mg kg(-1)) and organic phosphorus (P(o)) for 2 to 23% (130-1660 mg kg(-1)), respectively. In the NaHCO(3) fraction, P(i) varied between 740 and 4200 mg P kg(-1) DM (4-44% of total manure P), and P(o) varied between 340 and 1550 mg P kg(-1) DM (2-27% of total manure P). In the NaOH fraction, P(i) fluctuated around 200 mg P kg(-1) DM, and P(o) ranged from 130 to 630 mg P kg(-1) DM. Of the enzymatically hydrolyzable P(o) in the three fractions, phytate-like P dominated, measuring 26 to 605 mg kg(-1) DM, whereas monoester P and DNA-like P were relatively low and less variable. Although concentrations of various P forms varied considerably, significant correlations between manure total P and certain P forms were observed. For example, H(2)O-extracted P(i) was correlated with total manure P (R(2) = 0.62), and so was NaOH-extracted P(o) (R(2) = 0.81). Data also show that the amount of P released by a single extraction with sodium acetate (100 mM, pH 5.0) was equivalent to the sum of P in all three fractions (H(2)O-, NaHCO(3)-, and NaOH-extractable P). Thus, a single extraction by sodium acetate buffer could provide an efficient evaluation of plant-available P in animal manure, while the sequential fractionation approach provides more detailed characterization of manure P.     

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.     

Investigation of the inorganic and organic phosphorus forms in animal manure

The most viable way to beneficially use animal manure on most farms is land application. Over the past few decades, repeated manure application has shown adverse effects on environmental quality due to phosphorus (P) runoff with rainwater, leading to eutrophication of aquatic ecosystems. Improved understanding of manure P chemistry may reduce this risk. In this research, 42 manure samples from seven animal species (beef and dairy cattle, swine, chicken, turkey, dairy goat, horse, and sheep) were sequentially fractionated with water, NaHCO?, NaOH, and HCl. Inorganic (P(i)), organic (P(o)), enzymatic hydrolyzable (P(e); monoester-, DNA-, and phytate-like P), and nonhydrolyzable P were measured in each fraction. Total dry ash P (P(t)) was measured in all manures. Total fractionated P (P(ft)) and total P(i) (P(it)) showed a strong linear relationship with P(t). However, the ratios between P(ft)/P(t) and P(it)/P(t) varied from 59 to 117% and from 28 to 96%, respectively. Water and NaHCO? extracted most of the P(i) in manure from ruminant+horse, whereas in nonruminant species a large fraction of manure P was extracted in the HCl fraction. Manure P(e) summed over all fractions (P(et)) accounted for 41 to 69% of total P(0) and 4 to 29% of P(t). The hydrolyzable pool in the majority of the manures was dominated by phytate- and DNA-like P in water, monoester- and DNA-like P in NaHCO?, and monoester- and phytate-like P in NaOH and HCl fractions. In conclusion, if one assumes that the P(et) and P(it) from the fractionation can become bioavailable, then from 34 to 100% of P(t) in animal manure would be bioavailable. This suggests the need for frequent monitoring of manure P for better manure management practices.     

Efficacy of alum and coal combustion by-products in stabilizing manure phosphorus

Animal manures contain large amounts of soluble phosphorus (P), which is prone to runoff losses when manure is surface-applied. Here we report the efficacy of alum and three coal combustion by-products in reducing P solubility when added to dairy, swine, or broiler litter manures in a laboratory incubation study. Compared with unamended controls, alum effectively reduced readily soluble P, determined in water extracts of moist manure samples with 1 h of shaking, for all three manures. The reduction ranged from 80 to 99% at treatment rates of 100 to 250 g alum kg(-1) manure dry matter. The fluidized bed combustion fly ash (FBC) reduced readily soluble P by 50 to 60% at a rate of 400 g kg(-1) for all three manures. Flue gas desulfurization by-product (FGD) reduced readily soluble P by nearly 80% when added to swine manure and broiler litter at 150 and 250 g kg(-1). Another by-product, anthracite refuse fly ash (ANT), was ineffective for all three manures. In all cases, reduction in readily soluble P is primarily associated with inorganic phosphorus (P(i)) with little change in organic phosphorus (P(o)). Sequential extraction results indicate that the by-product treatments shifted manure P from H2O-P into a less vulnerable fraction, NaHCO3 - P, while the alum treatment shifted the P into even more stable forms, mostly NaOH-P. Such shifts in P fractions would have little influence on P availability for crops over the long-term but would retard and reduce potential losses of P following manure applications.     

Predicting phosphorus availability from soil-applied composted and non-composted cattle feedlot manure

Prediction of phosphorus (P) availability from soil-applied composts and manure is important for agronomic and environmental reasons. This study utilized chemical properties of eight composted and two non-composted beef cattle (Bos taurus) manures to predict cumulative phosphorus uptake (CPU) during a 363-d controlled environment chamber bioassay. Ten growth cycles of canola (Brassica napus L.) were raised in pots containing 2 kg of a Dark Brown Chernozemic clay loam soil (fine-loamy, mixed, Typic Haploboroll) mixed with 0.04 kg of the amendments. Inorganic P fertilizer (KH2PO4) and an unamended control were included for comparison. All treatments received a nutrient solution containing an adequate supply of all essential nutrients, except P, which was supplied by the amendments. Cumulative P uptake was similar for composted (74 mg kg-1 soil) and non-composted manures (60 mg kg-1 soil) and for the latter and the fertilizer (40 mg kg-1 soil). However, the CPU was significantly higher for organic amendments than the control (24 mg kg-1 soil) and for composted manure than the fertilizer. Apparent phosphorus recovery (APR) from composted manure (24%) was significantly lower than that from non-composted manure (33%), but there was no significant difference in APR between the organic amendments and the fertilizer (27%). Partial least squares (PLS) regression indicated that only two parameters [total water-extractable phosphorus (TPH2O) and total phosphorus (TP) concentration of amendments] were adequate to model amendment-derived cumulative phosphorus uptake (ACPU), explaining 81% of the variation in ACPU. These results suggest that P availability from soil-applied composted and non-composted manures can be adequately predicted from a few simple amendment chemical measurements. Accurate prediction of P availability and plant P recovery may help tailor manure and compost applications to plant needs and minimize the buildup of bioavailable P, which can contribute to eutrophication of sensitive aquatic systems.     

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.     

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.     

Phosphorus extractability of soils amended with stockpiled and composted cattle manure

Managing fertilizer applications to maintain soil P below environmentally unacceptable levels should consider the contribution of manure and synthetic fertilizer sources to soluble and extractable forms of P. Our objective was to evaluate soil and manure characteristics and application rates on P extractability in recently amended soils. Five soils of the U.S. southern High Plains were amended with beef cattle manures, composted beef manure, and inorganic fertilizers [Ca(H(2)PO(4))(2) or KH(2)PO(4)] at five rates and incubated under controlled conditions. Mehlich 3-, Olsen (NaHCO(3))-, Texas A&M extractant (TAM)-, and water-extractable P were determined for the soils after selected incubation periods. Except for TAM and some water extractions, P extractability as a function of total P applied was linear (P < 0.001) for a wide range of application rates. Mehlich-3, NaHCO(3), and water P extraction efficiencies of KH(2)PO(4)-amended soils averaged 22, 34, and 115% greater (P < or = 0.036), respectively, than efficiencies of soils amended with manures except for the Texline (calcareous) loam and Pullman clay loam soils. Phosphorus extraction efficiencies decreased with time for KH(2)PO(4)-amended soils (P < 0.05) but remained stable or increased for manure-amended soils during the 8-wk incubation period. Across all soils and manure sources, changes in water-extractable P per unit increase in Mehlich 3-, NaHCO(3)-, and TAM-extractable P averaged 100, 85, and 125% greater, respectively, for inorganic as compared with manure-amended soils. These source-dependent relationships limit the use of agronomic soil extractants to make correct inferences about water-extractable P and dissolved P in runoff.     

Runoff phosphorus losses from surface-applied biosolids

Runoff losses of dissolved and particulate phosphorus (P) may occur when rainfall interacts with manures and biosolids spread on the soil surface. This study compared P levels in runoff losses from soils amended with several P sources, including 10 different biosolids and dairy manure (untreated and treated with Fe or Al salts). Simulated rainfall (71 mm h(-1)) was applied until 30 min of runoff was collected from soil boxes (100 x 20 x 5 cm) to which the P sources were surfaced applied. Materials were applied to achieve a common plant available nitrogen (PAN) rate of 134 kg PAN ha(-1), resulting in total P loading rates from 122 (dairy manure) to 555 (Syracuse N-Viro biosolids) kg P ha(-1). Two biosolids produced via biological phosphorus removal (BPR) wastewater treatment resulted in the highest total dissolved phosphorus (13-21.5 mg TDP L(-1)) and total phosphorus (18-27.5 mg TP L(-1)) concentrations in runoff, followed by untreated dairy manure that had statistically (p = 0.05) higher TDP (8.5 mg L(-1)) and TP (10.9 mg L(-1)) than seven of the eight other biosolids. The TDP and TP in runoff from six biosolids did not differ significantly from unamended control (0.03 mg TDP L(-1); 0.95 mg TP L(-1)). Highest runoff TDP was associated with P sources low in Al and Fe. Amending dairy manure with Al and Fe salts at 1:1 metal-to-P molar ratio reduced runoff TP to control levels. Runoff TDP and TP were not positively correlated to TP application rate unless modified by a weighting factor reflecting the relative solubility of the P source. This suggests site assessment indices should account for the differential solubility of the applied P source to accurately predict the risk of P loss from the wide variety of biosolids materials routinely land applied.     

Enzymatic hydrolysis of organic phosphorus in swine manure and soil

Organic phosphorus (Po) exists in many chemical forms that differ in their susceptibility to hydrolysis and, therefore, bioavailability to plants and microorganisms. Identification and quantification of these forms may significantly contribute to effective agricultural P management. Phosphatases catalyze reactions that release orthophosphate (Pi) from Po compounds. Alkaline phosphatase in tris-HCl buffer (pH 9.0), wheat (Triticum aestivum L.) phytase in potassium acetate buffer (pH 5.0), and nuclease P1 in potassium acetate buffer (pH 5.0) can be used to classify and quantify Po in animal manure. Background error associated with different pH and buffer systems is observed. In this study, we improved the enzymatic hydrolysis approach and tested its applicability for investigating Po in soils, recognizing that soil and manure differ in numerous physicochemical properties. We applied (i) acid phosphatase from potato (Solanum tuberosum L.), (ii) acid phosphatases from both potato and wheat germ, and (iii) both enzymes plus nuclease P1 to identify and quantify simple labile monoester P, phytate (myo-inositol hexakis phosphate)-like P, and DNA-like P, respectively, in a single pH/buffer system (100 mM sodium acetate, pH 5.0). This hydrolysis procedure released Po in sequentially extracted H2O, NaHCO3, and NaOH fractions of swine (Sus scrofa) manure, and of three sandy loam soils. Further refinement of the approach may provide a universal tool for evaluating hydrolyzable Po from a wide range of sources.     

Establishing a linkage between phosphorus forms in dairy diets, feces, and manures

Effective manure management to efficiently utilize organic wastes without causing environmental degradation requires a clear understanding of the transformation of P forms from diet to manure. Thus, the objective of this study was to establish quantitative relationships between P forms in diets, feces, and manures collected from U.S. Northeastern and Mid-Atlantic commercial dairy farms. Total P in diets ranged from 3.6 to 5.3 g kg(-1) dry matter, while the feces had higher P than diets (5.7-9.5 g kg(-1)) and manures had lower P (2.5-8.9 g kg(-1)) than feces. The farms with total dietary P of 4.8 to 5.3 g P kg(-1) had twofold higher concentrations of phytic acid (1647-2300 mg P kg(-1)) than farms with 3.6 to 4.0 g dietary P kg(-1) (844-1100 mg P kg(-1)). Much of the phytic acid in diets was converted to inorganic orthophosphate in the rumen as indicated by a reduction in phytic acid percentage from diets (32%) to feces (18%). The proportion of orthophosphate diesters (phospholipids, deoxyribonucleic acid [DNA]) was twice as high in feces (6.2-10%) as diets (2.4-5.3%) suggesting the excretion of microbial residues in feces. Phosphonates (aminoethyl phosphonates and phosphonolipids) were not seen in diets but were detected in feces and persisted in manures, which suggests a microbial origin. These organic compounds (phytic acid, phospholipids, DNA) were decomposed on storage of feces in slurry pits, increasing orthophosphate in manures by 9 to 12% of total P. These results suggest that reducing dietary P and typically storing feces in dairy farms will result in manure with similar chemical forms (primarily orthophosphate: 63-77%) that will be land applied. Thus, both the reduction of dietary P and storage of manure on farm are important for controlling solubility and bioavailability of P forms in soils and waters.     

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.     

Chemical fractionation of phosphorus in stabilized biosolids

Three chemicals-ferrous sulfate (FeSul), calcium oxide (CaO), and aluminum sulfate (alum)-were applied at different rates to stabilize P in fresh, anaerobically digested biosolids (FBS) obtained from an activated sewage treatment plant. A modified Hedley fractionation procedure was used to assess P forms in these sludge-borne materials and in a biosolids compost (BSC) prepared from the same FBS. Each biosolids material exhibited a unique pattern of P distribution among fractions. The most available P forms, namely: (i) water-soluble P (WSP); (ii) membrane-P; and (iii) NaHCO(3)-P, were stabilized by small rates of each of the chemicals; but the P transformation into more stable forms depended on the type of chemical added. The stabilized P forms were enhanced by high rates of CaO and FeSul, but were reduced by high rates of alum. The organic P (P(o)) in the first three fractions of the FeSul- and alum-stabilized biosolids was enhanced by the chemical addition, and P(o) transformation from NaOH-P(o) into NaHCO(3)-P(o) was found in calcium-stabilized biosolids. A positive relationship was found between NaHCO(3)-P(o) and the NaHCO(3)-extracted organic C in all chemically stabilized biosolids. One-step extraction by NaHCO(3) or NaOH underestimated P extraction compared to the stepwise extraction. The reported results are consistent with solid-state P speciation reported earlier and contribute important information for optimizing biosolids stabilization to reduce P loss after incorporation in soils and for maximizing soil capacity to safely store pre-stabilized biosolids.     

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.     

Phosphorus saturation in spodosols impacted by manure

Significant amounts of phosphorus (P) accumulate in soils receiving animal manures that could eventually result in unacceptable concentrations of dissolved P loss through surface runoff or subsurface leaching. The degree of phosphorus saturation (DPS) relates a soil's extractable P to its P sorbing capacity, and is reportedly a predictor of the P likely to be mobilized from a system. A DPS value (DPS-1) was derived that expressed the percentage of Mehlich 1-extractable P to the sorbing capacity of a Spodosol (expressed as the sum of oxalate-extractable Fe and Al). Values of DPS-1 were determined in various horizons of soil in current and abandoned dairy systems in South Florida's Lake Okeechobee watershed to assess P release potential. Land use within the dairies was classified as highly impacted by cattle (intensive and holding), and minimally impacted by cattle (pasture, forage, or native) areas. The A and E horizon of soils in heavily manure-impacted intensive and holding areas for both active and abandoned dairies generally had higher DPS-1 values than the pasture, forage, and native area soils, which were minimally impacted by manure. Degree of P saturation was also calculated as a percentage of Mehlich 1-extractable P to the sum of Mehlich 1-extractable Fe and Al (DPS-2). Both DPS-1 and DPS-2 were shown to be significantly (P = 0.0001) related to water-extractable P for all soil horizons, suggesting that either index can be used as an indicator for P loss potential from a soil.     

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.     

Particulate and dissolved phosphorus chemical separation and phosphorus release from treated dairy manure

In confined animal feeding operations, liquid manure systems present special handling and storage challenges because of the large volume of diluted wastes. Water treatment polymers and mineral phosphorus (P) immobilizing chemicals [AI2(SO4)3 x 18H2O, FeCl3-6H2O, and Class C fly ash] were used to determine particulate and dissolved reactive phosphorus (DRP) reduction mechanisms in high total suspended solid (TSS) dairy manure and the P release from treated manure and amended soils. Co-application exceeded the aggregation level achieved with individual manure amendments and resulted in 80 and 90% reduction in metal salt and polymer rates, respectively. At marginally effective polymer rates between 0.01 and 0.25 g L(-1), maximal aggregation was attained in combination with 1 and 10 g L(-1) of aluminum sulfate (3 and 30 mmol Al3+ L(-1)) and iron chloride (3.7 and 37 mmol Fe3+ L(-1)) in 30 g L(-1) (TSS30) and 100 g L(-1) TSS (TSS100) suspensions, respectively. Fly ash induced particulate destabilization at rates > or = 50 g L(-1) and reduced solution-phase DRP at all rates > or = 1 g L(-1) by 52 and 71% in TSS30 and TSS100 suspensions, respectively. Aluminum and Fe salts also lowered DRP at rates < or = 10 g L(-1) and higher concentrations redispersed particulates and increased DRP due to increased suspension acidity and electrical conductivity. The DRP release from treated manure solids and a Typic Paleudult amended with treated manure was reduced, although the amendments increased Mehlich 3-extractable P. Therefore, the synergism of flocculant types allowed input reduction in aggregation aid chemicals, enhancing particulate and dissolved P separation and immobilization in high TSS liquid manure.     

Determination of phosphorus source coefficients for organic phosphorus sources: laboratory studies

Phosphorus losses in runoff from application of manures and biosolids to agricultural land are implicated in the degradation of water quality in the Chesapeake and Delaware Inland Bays. We conducted an incubation study to determine the relative P solubility and bioavailability, referred to as P source coefficients (PSCs), for organic P sources, which are typically land-applied in the Mid-Atlantic USA. Nine organic and one inorganic (KH2PO4) P amendments were applied to an Evesboro loamy sand (mesic, coated Typic Quartzipsamments) at a rate of 60 mg P kg(-1) and incubated for 8 wk with subsamples analyzed at 2 and 8 wk. There was an increase in Mehlich-3 P (M3-P), water-soluble P (WS-P), iron-oxide strip extractable P (FeO-P), and Mehlich-3 P saturation ratio (M3-PSR) with P additions, which varied by P source. The trend of relative extractable WS-P, FeO-P, and M3-P generally followed the pattern: inorganic P > liquid and deep pit manures > manures and biosolids treated with metal salts or composted. We found significant differences in the availability of P from varying organic P sources. The use of PSCs may be beneficial when determining the risk of P losses from land application of manures and other organic P sources and could be used in risk assessments such as a P site index. These PSCs may also be useful for determining P application rates when organic P sources are applied to P deficient soils for use as a fertilizer source.