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.     

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.     

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.     

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.     

Runoff losses of sediment and phosphorus from no-till and cultivated soils receiving dairy manure

Managing manure in no-till systems is a water quality concern because surface application of manure can enrich runoff with dissolved phosphorus (P), and incorporation by tillage increases particulate P loss. This study compared runoff from well-drained and somewhat poorly drained soils under corn (Zea mays, L.) production that had been in no-till for more than 10 yr. Dairy cattle (Bos taurus L.) manure was broadcast into a fall planted cover crop before no-till corn planting or incorporated by chisel/disk tillage in the absence of a cover crop. Rainfall simulations (60 mm h(-1)) were performed after planting, mid-season, and post-harvest in 2007 and 2008. In both years and on both soils, no-till yielded significantly less sediment than did chisel/disking. Relative effects of tillage on runoff and P loss differed with soil. On the well-drained soil, runoff depths from no-till were much lower than with chisel/disking, producing significantly lower total P loads (22-50% less). On the somewhat poorly drained soil, there was little to no reduction in runoff depth with no-till, and total P loads were significantly greater than with chisel/disking (40-47% greater). Particulate P losses outweighed dissolved P losses as the major concern on the well-drained soil, whereas dissolved P from surface applied manure was more important on the somewhat poorly drained soil. This study confirms the benefit of no-till to erosion and total P runoff control on well-drained soils but highlights trade-offs in no-till management on somewhat poorly drained soils where the absence of manure incorporation can exacerbate total P losses.     

Nitrogen- vs. phosphorus-based dairy manure applications to field crops: nitrate and phosphorus leaching and soil phosphorus accumulation

Management of animal manures to provide nutrients for crop growth has generally been based on crop N needs. However, because manures have a lower N/P ratio than most harvested crops, N-based manure management often oversupplies the crop-soil system with P, which can be lost into the environment and contribute to eutrophication of water bodies. We examined the effects of N- vs. P-based manure applications on N and P uptake by alfalfa (Medicago sativa L.), corn (Zea mays L.) for silage, and orchardgrass (Dactylis glomerata L.), leaching below the root zone, and accumulation of P in soil. Treatments included N- and P-based manure rates, with no nutrient input controls and inorganically fertilized plots for comparison. Nitrate concentrations in leachate from inorganic fertilizer or manure treatments averaged 14 mg NO(3)-N L(-1), and did not differ by nutrient treatment. Average annual total P losses in leachate did not exceed 1 kg ha(-1). In the top 5 cm of soil in plots receiving the N-based manure treatment, soil test P increased by 47%, from 85 to 125 mg kg(-1). Nitrogen- and P-based manure applications did not differ in ability to supply nutrients for crop growth, or in losses of nitrate and total P in leachate. However, the N-based manure led to significantly greater accumulation of soil test P in the surface 5 cm of soil. Surface soil P accumulation has implications for increased risk of off-field P movement.     

Estimates of residual dairy manure nitrogen availability using various techniques

It is common practice to repeatedly apply dairy manure to the same fields. To accurately assess the total plant availability of manure nutrients, it is necessary to account for the nutrients remaining in soil from previous manure applications. A field experiment studying manure nitrogen (N) uptake by corn (Zea mays L.) was conducted from 1998 to 2003 on a Plano silt loam (fine-silty, mixed, mesic, Typic Argiudolls). Plots received two rates of semisolid manure either every year, every 2 yr, or every 3 yr to estimate first-, second-, and third-year dairy manure N residuals. Residual manure N availability was estimated from single and multiple manure applications using (i) the fertilizer N equivalence method, (ii) the apparent recovery (difference) method, (iii) relative effectiveness method, and (iv) recovery of (15)N-labeled manure. Second-year availabilities after a single manure application using the fertilizer equivalence, difference, and relative effectiveness methods were estimated to be 12, 8, and 4% of total manure N applications, respectively. Estimates of third-year availability by these methods were 3, 1, and 5%, respectively. Measurement of (15)N recovered from labeled manure was 6 and 2% in the second and third year, respectively. Fertilizer equivalence, difference, and relative effectiveness methods showed great year to year variability, reducing the confidence in the residual manure N availability estimates by these methods, but using (15)N-labeled manures reduced variability substantially. Based on this and other studies, we suggest that second- and third-year residual N availability from a single application of semisolid dairy manure would be 9 to 12%, and 3 to 5% of the original manure N application, respectively.     

Determination of steroidal estrogens in flushed dairy manure wastewater by gas chromatography-mass spectrometry

There is a critical need to accurately measure the concentrations of natural steroidal estrogens in flushed dairy manure wastewater (FDMW) to assess any potential risk of waterway contamination resulting from land application. Estrogens are a concern because low concentrations (10-100 ng L-1) in water can adversely affect aquatic vertebrate species such as fish, turtles, and frogs by disrupting the normal function of their endocrine systems. The objective of this study was to develop a sample preparation method that permits the quantification of four natural steroidal estrogens (17alpha-estradiol, 17beta-estradiol, estrone, and estriol) in FDMW by gas chromatography-mass spectrometry (GC-MS). Solid-phase extraction with graphitized carbon black was used for the bulk extraction of estrogens from FDMW and additional sample purification was accomplished with C-18. The sample preparation method allowed estrogens to be detected accurately by GC-MS in FDMW. Spiked recovery experiments indicated that the method is satisfactory for measuring the estrogens of interest in FDMW with average recovery of >90%. As expected in FDMW, characterization of the estrogen profile revealed a large abundance of 17alpha-estradiol relative to 17beta-estradiol and estrone. Estriol was not detected in FDMW. The methodology developed in this research helps provide an analytical foundation for the quantification of steroidal estrogens in FDMW by GC-MS.     

Enhanced transformation of lead speciation in rhizosphere soils using phosphorus amendments and phytostabilization: an x-ray absorption fine structure spectroscopy investigation

To formulate successful phytostabilization strategies in a shooting range soil, understanding how heavy metals are immobilized at the molecular level in the rhizosphere soil is critical. Lead (Pb) speciation and solubility in rhizosphere soils of five different plant species were investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy and chemical extraction. The EXAFS analysis indicated that Pb occurred as PbCO (37%), Pb sorbed to organic matter (Pb-org: 15%), and Pb sorbed to pedogenic birnessite and/or ferrihydrite (Pb-ox: 36%) in the bulk soil. Comparison of the EXAFS spectra between bulk and rhizosphere soils demonstrated notable differences in fine structure, indicating that Pb species had been modified by rhizosphere processes. The estimated proportion of PbCO (25%) in the buckwheat soil was smaller than the other rhizosphere soils (35-39%). The addition of P significantly reduced Pb solubility in the bulk and rhizosphere soil except in the rhizosphere of buckwheat, for which the Pb solubility was 10-fold greater than in the other P-amended soils. This larger solubility in the buckwheat rhizosphere could not be explained by the total Pb speciation in the soil but was presumably related to the acidifying effect of buckwheat, resulting in a decrease of the soil pH by 0.4 units. The reduced Pb solubility by P amendment resulted from the transformation of preexisting PbCO (37%) into Pb(PO)Cl (26-32%) in the bulk and rhizosphere soils. In the P-amended rhizosphere soils, Pb-org species were no longer detected, and the Pb-ox pool increased (51-57%). The present study demonstrated that rhizosphere processes modify Pb solubility and speciation in P-amended soils and that some plant species, like buckwheat, may impair the efficiency of Pb immobilization by P amendments.     

Effect of mineral and manure phosphorus sources on runoff phosphorus

Concern over nonpoint-source phosphorus (P) losses from agricultural lands to surface waters has resulted in scrutiny of factors affecting P loss potential. A rainfall simulation study was conducted to quantify the effects of alternative P sources (dairy manure, poultry manure, swine slurry, and diammonium phosphate), application methods, and initial soil P concentrations on runoff P losses from three acidic soils (Buchanan-Hartleton, Hagerstown, and Lewbeach). Low P (12 to 26 mg kg(-1) Mehlich-3 P) and high P (396 to 415 mg kg(-1) Mehlich-3 P) members of each soil were amended with 100 kg total P ha(-1) from each of the four P sources either by surface application or mixing, and subjected to simulated rainfall (70 mm h(-1) to produce 30 min runoff). Phosphorus losses from fertilizer and manure applied to the soil surface differed significantly by source, with dissolved reactive phosphorus (DRP) accounting for 64% of total phosphorus (TP) (versus 9% for the unamended soils). For manure amended soils, these losses were linearly related to water-soluble P concentration of manure (r2 = 0.86 for DRP, r2 = 0.78 for TP). Mixing the P sources into the soil significantly decreased P losses relative to surface P application, such that DRP losses from amended, mixed soils were not significantly different from the unamended soil. Results of this study can be applied to site assessment indices to quantify the potential for P loss from recently manured soils.     

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.     

Export of manure phosphorus and nitrogen in turfgrass sod

Regulatory mandates have increased demand for best management practices (BMPs) that will reduce nutrient loading on watersheds impaired by excess manure P and N. Export of manure P and N in turfgrass sod harvests is one BMP under consideration. This study quantified amounts and percentages of P and N removed in a sod harvest for different rates of manure and inorganic P and N. Six treatments comprised an unfertilized control, two manure rates with and without supplemental inorganic N, and inorganic P and N only. The treatments were applied to 'Tifway' bermudagrass (Cynodon dactylon L. x C. transvaalensis Burtt-Davey), '609' buffalograss [Buchloe dactyloides (Nutt.) Engelm.], and 'Reveille' bluegrass (Poa arachnifera Torr. x P. pratensis L.) under field conditions. Comparisons among treatments revealed small variations of P and N content in clippings and the plant component of sod, but large variations in the soil component of sod for each turf species. In addition, 2 to 10 times more P and 1.3 to 5 times more N was removed in soil than in plant components of sod for the two manure rates with and without added inorganic N. Percentages of applied P and N in harvested sod were similar for the two manure rates with and without added N for each species, but differed among turf species for each P (46 to 77%) and N (36 to 47%). The large amounts and percentages of manure P and N removed by sod harvest support the feasibility of this BMP in efforts to reduce nutrient loads on watersheds.     

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.     

Surface runoff losses of phosphorus from Virginia soils amended with turkey manure using phytase and high available phosphorus corn diets

Many states have passed legislation that regulates agricultural P applications based on soil P levels and crop P uptake in an attempt to protect surface waters from nonpoint P inputs. Phytase enzyme and high available phosphorus (HAP) corn supplements to poultry feed are considered potential remedies to this problem because they can reduce total P concentrations in manure. However, less is known about their water solubility of P and potential nonpoint-source P losses when land-applied. This study was conducted to determine the effects of phytase enzyme and HAP corn supplemented diets on runoff P concentrations from pasture soils receiving surface applications of turkey manure. Manure from five poultry diets consisting of various combinations of phytase enzyme, HAP corn, and normal phytic acid (NPA) corn were surface-applied at 60 kg P ha(-1) to runoff boxes containing tall fescue (Festuca arundinacea Schreb.) and placed under a rainfall simulator for runoff collection. The alternative diets caused a decrease in manure total P and water soluble phosphorus (WSP) compared with the standard diet. Runoff dissolved reactive phosphorus (DRP) concentrations were significantly higher from HAP manure-amended soils while DRP losses from other manure treatments were not significantly different from each other. The DRP concentrations in runoff were not directly related to manure WSP. Instead, because the mass of manure applied varied for each treatment causing different amounts of manure particles lost in runoff, the runoff DRP concentrations were influenced by a combination of runoff sediment concentrations and manure WSP.     

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.     

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.     

Water-soluble and solid-state speciation of phosphorus in stabilized sewage sludge

Three chemicals, ferrous sulfate (Fe-sul), calcium oxide (CaO), and aluminum sulfate (alum), were used to stabilize phosphorus (P) in fresh, anaerobically digested sewage sludge (FSS). The chemically stabilized sludge materials and biosolids compost (BSC) were compared with the FSS with respect to water-soluble phosphorus (WSP) content in its inorganic (WSP(i)) and organic (WSP(o)) forms as well as water-soluble organic carbon (DOC). Solid-state P speciation was further probed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with energy-dispersive X-ray elemental spectrometry (EDXS). Water-soluble P was effectively controlled by a wide range of Fe-sul or CaO additions to the sludge (Ca to P ratio = 3.47-17.72, Fe to P ratio = 1.01-16.53), but by only a narrow range (Al to P ratio = 1.04-2.87) of alum addition. The WSP content in the BSC was also depressed, but to a lesser extent. The pH in the treated sludge ranged from 3.0 to 12.5 and served as a key factor to control P chemistry. No correlation was observed between DOC and WSP(o). No crystallized Ca-P minerals were detected in the CaO-stabilized sludge, but brushite crystallization seemed to be obtained by low addition of Fe-sul and alum. Variscite and strengite crystallization was obtained following high addition of Fe-sul or alum, as detected by XRD and SEM-EDXS. Adsorption of P by newly formed Fe-hydroxide seems to play an important role in the Fe-sul-stabilized sludge. We concluded that administration of the tested chemicals at the proper rate can effectively reduce the hazard of P release and leaching from sludge.     

Influence of phytase on water-soluble phosphorus in poultry and swine manure

The effect of dietary non-phytin phosphorus (NPP) and phytase (PHY) concentration on total phosphorus (TP) and water-soluble phosphorus (WSP) excretion was determined. Diets tested in broiler experiments were: National Research Council nutrient requirements for non-phytin phosphorus (NRC), NRC + PHY, reduced non-phytin phosphorus (RED), and RED + PHY. Turkey and swine experiment diets included NRC, RED, and RED + PHY. For all experiments, except broiler Experiment 1, excreta were: (i) boiled, antibiotic added, then frozen; (ii) boiled, antibiotic added, incubated (37 degrees C for 72 h), then frozen; and (iii) incubated, boiled, antibiotic added, then frozen. In Experiment 1, excreta were collected and frozen or incubated for 24 or 48 h. In broiler Experiment 1, WSP was not affected by phytase but increased with post-excretion incubation. In a broiler Experiment 2, reducing NPP resulted in reduced excreta TP and WSP (11.3 to 8.3 and 5.3 to 2.7 g kg(-1)). Feeding RED + PHY diets resulted in less TP and WSP (7.6 and 0.6 g kg(-1)) as compared with NRC + PHY (11.2 and 3.9 g kg(-1), Experiment 3). Incubation resulted in increased WSP, irrespective of phytase addition such that WSP as a percent of TP was similar among treatments. Addition of antibiotics before incubation prevented the increase in WSP. Similar results were observed with turkey and swine. Therefore, when phytase is used properly (i.e., with a simultaneous reduction of NPP), WSP or WSP as a percent of TP are not affected. The increase in WSP as a percent of TP post-excretion is a function of excreta microbial activity and not dietary phytase addition.     

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.     

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.