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.     

Laboratory characterization of phosphorus in fresh and oven-dried organic amendments

This study was performed to determine the forms of P and to examine the influence of oven-drying on P forms in different organic amendments. Samples of biosolids, beef and dairy cattle manures, and hog manures from sow and nursery barns were used in this study. Both fresh and oven-dried amendments were analyzed for inorganic (Pi), organic (Po), and total phosphorus using a modified Hedley fractionation technique. Water extracted about 10% of total biosolids P and 30 to 40% of total hog and cattle manure P. The amount of P extracted by NaHCO3 ranged from 21 to 32% of total P in all organic amendments except in the dairy cattle manure with 45% of total P. The labile P fraction (sum of H2O- and NaHCO3-extractable P) was 24% of biosolids P, 60% of hog manure P, and 70% of dairy cattle manure P. The residual P was about 10% in biosolids and cattle manures and 5 to 8% in hog manures. Oven-drying caused a transformation in forms of P in the organic amendments. In hog manures, H2O-extractable Po was transformed to Pi, while in the dairy manure NaHCO3-extractable P was converted to H2O-extractable Pi with oven-drying. Therefore, caution should be exercised in using oven-drying for studies that evaluate forms of P in organic amendments. Overall, these results indicate that biosolids P may be less susceptible to loss by water when added to agricultural land.     

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.     

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.     

Effect of broadcast manure on runoff phosphorus concentrations over successive rainfall events

Concern over eutrophication has directed attention to manure management effects on phosphorus (P) loss in runoff. This study evaluates the effects of manure application rate and type on runoff P concentrations from two, acidic agricultural soils over successive runoff events. Soils were packed into 100- x 20- x 5-cm runoff boxes and broadcast with three manures (dairy, Bos taurus, layer poultry, Gallus gallus; swine, Sus scrofa) at six rates, from 0 to 150 kg total phosphorus (TP) ha(-1). Simulated rainfall (70 mm h(-1)) was applied until 30 min of runoff was collected 3, 10, and 24 d after manure application. Application rate was related to runoff P (r2 = 0.50-0.98), due to increased concentrations of dissolved reactive phosphorus (DRP) in runoff; as application rate increased, so did the contribution of DRP to runoff TP. Varied concentrations of water-extractable phosphorus (WEP) in manures (2-8 g WEP kg(-1)) resulted in significantly lower DRP concentrations in runoff from dairy manure treatments (0.4-2.2 mg DRP L(-1)) than from poultry (0.3-32.5 mg DRP L(-1)) and swine manure treatments (0.3-22.7 mg DRP L(-1)). Differences in runoff DRP concentrations related to manure type and application rate were diminished by repeated rainfall events, probably as a result of manure P translocation into the soil and removal of applied P by runoff. Differential erosion of broadcast manure caused significant differences in runoff TP concentrations between soils. Results highlight the important, but transient, role of soluble P in manure on runoff P, and point to the interactive effects of management and soils on runoff P losses.     

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.     

Effect of poultry diet on phosphorus in runoff from soils amended with poultry manure and compost

Phosphorus in runoff from fields where poultry litter is surface-applied is an environmental concern. We investigated the effect of adding phytase and reducing supplemental P in poultry diets and composting poultry manures, with and without Fe and Al amendments, on P in manures, composts, and runoff. We used four diets: normal (no phytase) with 0.4% supplemental P, normal + phytase, phytase + 0.3% P, and phytase + 0.2% P. Adding phytase and decreasing supplemental P in diets reduced total P but increased water-extractable P in manure. Compared with manures, composting reduced both total P, due to dilution of manure with woodchips and straw, and water-extractable P, but beyond a dilution effect so that the ratio of water-extractable P to total P was less in compost than manure. Adding Fe and Al during composting did not consistently change total P or water-extractable P. Manures and composts were surface-applied to soil boxes at a rate of 50 kg total P ha(-1) and subjected to simulated rainfall, with runoff collected for 30 min. For manures, phytase and decreased P in diets had no significant effect on total P or molybdate-reactive P loads (kg ha(-1)) in runoff. Composting reduced total P and molybdate-reactive P loads in runoff, and adding Fe and Al to compost reduced total P but not molybdate-reactive P loads in runoff. Molybdate-reactive P in runoff (mg box(-1)) was well correlated to water-extractable P applied to boxes (mg box(-1)) in manures and composts. Therefore, the final environmental impact of dietary phytase will depend on the management of poultry diets, manure, and farm-scale P balances.     

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.     

Effect of varying the phosphorus content of dairy cow diets on losses of phosphorus in overland flow following surface applications of manure

The increasing use of concentrate feedstuffs within Northern Ireland dairy systems has resulted in significant farm gate phosphorus (P) surpluses, and these have contributed to increased soil P levels and risk of P loss to overland flow. However, the P content of feed concentrates can be lowered without compromising animal performance. This study focuses on P losses from grassland and evaluates how adjusting the P content of manure impacts on the P composition and concentration in overland flow. Dairy cows were offered diets containing 5.3 to 3.0 g P kg(-1) dry matter (DM) and produced manures with a range of P contents. Manure was applied at a rate of 50 m3 ha(-1) to 0.5-m2 grassland plots, and simulated rainfall (40 mm h(-1)) was applied repeatedly 2, 9, 28, and 49 d after during the summer, winter, and spring. Decreasing the P content in the diet, from the highest to the lowest P treatment (43%), produced a proportionately greater reduction in manure TP content (63%), but reductions were not exclusively in the water-soluble fraction. Following surface applications of manure, P concentrations in overland flow increased in all seasons (P < or = 0.001), while the greatest impact of varying the manure P content was most evident during the first simulated overland flow event. When diet P content was reduced from 5.4 to 3.0 g P kg(-1) DM, a statistically significant reduction in runoff P concentration was observed in all seasons. Elevated P concentrations in overland flow were observed for 28 d in spring and 9 d in summer and winter. The large drop in P concentrations between simulated rainfall events on Day 2 and Day 9 suggests that increasing the time interval between manure application and the generation of overland flow has a greater impact on P losses than does varying the dietary P content.     

Runoff losses of phosphorus and nitrogen imported in sod or composted manure for turf establishment

Nutrient loading on impaired watersheds can be reduced through export of sod grown with manure and export of composted manure for turf production on other watersheds. Effects of the sod and manure exports on receiving watersheds were evaluated through monitoring of total dissolved phosphorus (TDP) and N concentrations and losses in runoff from establishing turf. Three replications of seven treatments were established on an 8.5% slope of a Booneville soil (loamy-skeletal, mixed, superactive Pachic Argicryolls). Three treatments comprised imported 'Tifway' bermudagrass [Cynodon dactylon (L.) Pers. x C. transvaalensis Burtt-Davy) sod grown with composted dairy manure (382 or 191 kg P ha(-1)) or fertilizer (50 kg P ha(-1)). Three treatments were sprigged with Tifway and top-dressed with either composted manure (92 or 184 kg P ha(-1)) or fertilizer (100 kg P ha(-1)). The control was established bermudagrass [Cynodon dactylon (L.) Pers. var. Guymon]. During eight fall rain events, mean TDP concentration in runoff (7.8 mg L(-1)) from sprigged Tifway top-dressed with manure (84 kg P ha(-1)) was 1.6 times greater than sod imported with 129 kg manure P ha(-1). During the first fall event, mass losses of TDP (232 mg m(-2)) and total Kjeldahl nitrogen (TKN) (317 mg m(-2)) from sprigged treatments top-dressed with manure or fertilizer were nearly three times greater than manure-grown sod. Percentages of manure P lost as TDP in runoff from imported sod were 33% of percentages lost from sprigged treatments top-dressed with manure. Sod grown with manure P rates of 190 kg P ha(-1) can be imported without increasing runoff losses of TDP compared with conventional fertilization of establishing turfgrass.     

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.     

Sorption of inorganic and total phosphorus from dairy and swine slurries to soil

Understanding P sorption from animal manures is essential to formulate best management practices with regard to land application of manure from the standpoint of crop production and environmental quality. Little research has focused on the construction of P sorption isotherms where the P source is manure. The objectives of this study were to: (i) develop a procedure to characterize how inorganic P (P(i)) and total P (P(t)) from dairy slurry and swine slurry sorbs to soil; and (ii) compare the sorption characteristics of P(i) and P(t) where the P source was dairy slurry, swine slurry, or potassium phosphate (KH2PO4). Sorption solutions were prepared in 0.1 M KCl at pH 6 and equilibrated with soils at a 1:25 (w/v) soil/solution ratio for 24 h. Inorganic P, P(t), Al, and Fe in the equilibrated solutions were measured. For all soils, P(i) and P(t) sorption capacity of dairy slurry was greater than KH2PO4. Total P sorption capacity of swine slurry was greater than KH2PO4, while P(i) sorption capacity was less than KH2PO4. Overall, P(i) and P(t) sorption strengths of the manure slurries were less than or equal to KH2PO4. Increased P(i) sorption from dairy slurry was correlated with Fe and Al desorption. Reduction of P(i) sorption capacity from swine slurry was related to preferential sorption of organic P. Additional studies need to be conducted to determine how differences in P sorption between manures and fertilizer impact in-field P availability to a crop and potential for losses in runoff water.     

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.     

Phosphorus fractionation in manure from swine fed traditional and low-phytate corn diets

Traditional corn (Zea mays L.) (TC), the primary grain used in swine (Sus scrofa) diets, stores a majority of its P as phytate, which is largely unavailable for digestion by nonruminant animals. Low-phytate corn (LPC) contains similar amounts of total P but a smaller percentage of P as phytate. When fed to swine, LPC increases P utilization and reduces P content of manure. While differences in P content between manure from animals fed TC and LPC diets have been documented, solubility and lability of manure P have not been compared. Manure P was characterized in manure from swine fed either LPC or TC diets in 2000 and 2001. Total P was lower (20 vs. 34 g kg(-1)) and N to P ratio was higher (4.5 vs. 3.3) in LPC manure than in TC manure. Manures were sequentially extracted with deionized water, 0.5 M NaHCO3, 0.1 M NaOH, and 1.0 M HCl. Extracts were analyzed for inorganic and total P. Most P (approximately 80%) in the extracts was in the inorganic form. Concentration of P in the water-extractable fraction was lower for LPC manure (10.2 g kg(-1) in 2000 and 9.7 g kg(-1) in 2001) than for TC manure (13.6 g kg(-1) in 2000 and 17.0 g kg(-1) in 2001). Percentage of total P in each extract was in the order of: H2O (60%), HCl (22%), NaHCO3 (12%), NaOH (8%), and residue (<1%). Total P and distribution of P in extracts indicates swine are able to utilize more P contained in LPC feed but the composition of P excreted in LPC manure is similar to TC manure. Solubility, crop availability, and lability of P in LPC manure should be similar to that of TC manure.     

Impact of manure phosphorus fractions on phosphorus loss from manured soils after incubation

The risk of P loss from manured soils is more related to P fractions than total P concentration in manure. This study examined the impact of manure P fractions on P losses from liquid swine manure- (LSM), solid cattle manure- (SCM), and monoammonium phosphate- (MAP) treated soils. Manure or fertilizer was applied at 50 mg P kg soil, mixed, and incubated at 20°C for 6 wk to simulate the interaction between applied P and soil when P is applied well in advance of a high risk period for runoff. Phosphorus fractions in manure were determined using the modified Hedley fractionation scheme. We used simulated rainfall (75 mm h?1 for 1 h) to quantify P losses in runoff from two soils (sand and clay loam). The proportion of total labile P (total P in water+NaHCO fractions) in manure was significantly greater in LSM (70%) than SCM (44%). Mean dissolved reactive P (DRP) load in runoff over 60 min was greatest from MAP-treated soil (18.1 mg tray?1), followed by LSM- (14.0 mg tray?1) and SCM- (11.0 mg tray?1) treated soils, all of which were greater than mean DRP load from the check (5.2 mg tray?1). Total labile P (water+NaHCO) in manure was a more accurate predictor of runoff DRP loads than water extractable P, alone, for these two soils. Therefore, NaHCO extraction of manure P may be a useful tool for managing the risk of manure P runoff losses when manure is applied outside a high risk period for runoff loss.     

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.     

The effects of soil carbon on phosphorus and sediment loss from soil trays by overland flow

Soil chemical constituents influence soil structure and erosion potential. We investigated manure and inorganic fertilizer applications on soil chemistry (carbon [C] quality and exchangeable cations), aggregation, and phosphorus (P) loss in overland flow. Surface samples (0-5 cm) of a Hagerstown (fine, mixed, semiactive, mesic Typic Hapludalf) soil, to which either dairy or poultry manure or triple superphosphate had been applied (0-200 kg P ha(-1) yr(-1) for 5 yr), were packed in boxes (1 m long, 0.15 m wide, and 0.10 m deep) to field bulk density (1.2 g cm(-3)). Rainfall was applied (65 mm h(-1)), overland flow collected, and sediment and P loss determined. All amendments increased Mehlich 3-extractable P (19-177 mg kg(-1)) and exchangeable Ca (4.2-11.5 cmol kg(-1)) compared with untreated soil. For all treatments, sediment transport was inversely related to the degree of soil aggregation (determined as ratio of dispersed and undispersed clay; r = 0.51), exchangeable Ca (r = 0.59), and hydrolyzable carbohydrate (r = 0.62). The loss of particulate P and total P in overland flow from soil treated with up to 50 kg P ha(-1) dairy manure (9.9 mg particulate phosphorus [PPI, 15.1 mg total phosphorus [TP]) was lower than untreated soil (13.3 mg PP, 18.1 mg TP), due to increased aggregation and decreased surface soil slaking attributed to added C in manure. Manure application at low rates (<50 kg P ha(-1)) imparts physical benefits to surface soil, which decrease P loss potential. However, at greater application rates, P transport is appreciably greater (26.9 mg PP, 29.5 mg TP) than from untreated soil (13.3 mg PP, 18.1 mg TP).     

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.     

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.     

An examination of spin-lattice relaxation times for analysis of soil and manure extracts by liquid state phosphorus-31 nuclear magnetic resonance spectroscopy

Phosphorous (P)-31 nuclear magnetic resonance (NMR) spectroscopy is used in the analysis of P forms in extracts of soils and manures for environmental and agronomic purposes. Quantitative spectra require knowledge about spin-lattice relaxation times (T1) to ensure adequate delays between pulses. This paper determined T1 values of P forms in reconstituted (0.2 g in 0.7 mL(-1)) samples of freeze-dried 0.25 M NaOH plus 50 mM EDTA extracts of eight diverse soils (Aquept, Dystrochrept x 2, Hapludand, Rendoll, Udand, Haplostoll, and Orthod), three different manures (dairy cattle, deer, and sheep), and one epiphyte moss. Total concentrations in the reconstituted samples ranged from 5 to 175 mg Fe mL(-1), 2 to 62 mg Mn mL(-1), and 72 to 837 mg P mL(-1). Values of T1 for orthophosphate monoesters, orthophosphate diesters, and pyrophosphate varied from 0.42 to 1.69 s in soils and from 0.89 to 2.59 s in manures and the epiphyte. In contrast, T(1) for orthophosphate varied from 0.78 to 1.94 s in soils and 1.45 to 5.82 s in manures and the epiphyte. For quantitative 31P NMR, delay times should be three to five times the T1 value, translating to delays of 3 to 5 s for soils and up to 25 s for manures. If the required delay is too long then strategies such as adding paramagnetics could shorten T1, provided this does not increase line-broadening too much. A regression relationship was obtained between orthophosphate T1 values and the ratio of P concentration to Fe and Mn concentration on a w/v basis (r2= 0.97, P < 0.001), and between the T1 for all other compound classes and the ratio of P to Fe and Mn (r2= 0.70, P < 0.01). By combining measurement of Fe, Mn, and P in the reconstituted extract and these relationships, T1 can be estimated and the appropriate delay time used. If T1 is not considered and the delay time is too short, some peaks will be under- or over-represented and the relative distribution of P forms not quantitative.