Polyvalent cation effects on myo-inositol hexakis dihydrogenphosphate enzymatic dephosphorylation in dairy wastewater

Information is needed on organic polyphosphates such as myo-inositol 1,2,3,5/4,6-hexakis dihydrogenphosphate or phytate (IP6) contribution to the sources and sinks of dissolved phosphorus (PO4-P) in the soil-manure-water system. Effects of Na+, Ca2+, Al3+, and Fe3+ and cation to IP6-P mole ratios on the enzymatic dephosphorylation of IP6 were studied to determine controlling mechanisms of dephosphorylation and persistence in manure. Phytate- and PO4-P were analyzed by high-performance liquid chromatography. Phytate dephosphorylation by Aspergillus ficuum (Reichardt) Henn. phytase EC 3.1.3.8 decreases by 50 +/- 3.6 and 40 +/- 4% at pH 4.5 and 6, respectively, as Ca2+ concentrations increase and cation to IP6-P mole ratios reach 6:6. Polyanionic IP6 has a high affinity for Al3+ and Fe3+ and reductions in dephosphorylation average 27 and 32% at a cation to IP6-P mole ratio of 1:6 for Al3+ and Fe3+, respectively, while reaching more than 99% at a mole ratio of 6:6. A phytase-hydrolyzable phosphorus (PHP) fraction is native to ruminant animal manure and is proportional to total solids (TS) concentration in 1 to 100 g L(-1) suspensions. Added phytase, in effect, increases water-extractable P content of manure and the risk of environmental P dispersion. As the bioavailability and ecological effect of IP6-P appear to be regulated not only by pH-controlled enzyme activity but also by the associated counterions, the differential protective effects of cations influence the accuracy of manure PHP fraction estimates and increase phytate resistance to enzymatic dephosphorylation that may lead to its persistence in manure.     

Precipitation of liquid swine manure phosphates using magnesium smelting by-products

Swine manure contains considerable amounts of total (P) and soluble phosphorus (PO(4)-P) which may increase the soil P content when applied in excess to crop requirements and, consequently, risk water eutrophication. The feasibility of using magnesium (Mg) from the by-product of electrolysis and foundries (BPEF) for the removal of P from liquid swine manure was studied by adding up to 3 g of Mg as BPEF per liter of nursery (NU) and grower-finisher (GF) swine manure in 25-L plastic buckets. Changes in P and other elements were monitored for up to 360 h. Small amounts of Mg as BPEF (0.5 and 1.0 g Mg L(-1) manure) reduced the total P concentration of the liquid fraction by 70 to 95% of both manure types with respect to the control treatment of mixed raw manure. A settling period of 8 h or more was necessary to significantly reduce the liquid fraction's total P concentration for both manure types. Reduction of PO(4)-P varied from 96 to 100% in the liquid fractions for both manure types, which along with natural settling, explains most of the total P reduction in that fraction. The addition of BPEF did not influence the N content of manure. The low P liquid fraction can be safely applied to saturated P soils whereas the high P solid fraction offers the opportunity of transporting manure to agricultural soils deficient in P. Since N is conserved, both liquid and solid fractions could be valuable fertilizer manure by-products.     

Biosolids application in the Chihuahuan desert: effects on runoff water quality

Surface-applied biosolids, the option most often used on range-lands, can increase the concentration of macronutrients and trace elements in the runoff water and can potentially produce eutrophication or contamination of surface waters. In this study, the effects of postapplication age of biosolids (18, 12, 6, and 0.5 mo) and rate of application (0, 7, 18, 34, and 90 Mg ha(-1)) on the quality of runoff water from shrubland and grassland soils were assessed. Between July and October 1996 simulated rainfall was applied to 0.50-m2 plots for 30 min at a rate of 160 mm h(-1). All of the runoff water was collected. The concentration of NH4+ -N, NO3- -N, PO4(3-)-P, total dissolved phosphorus (TDP), Cu, and Mn in the runoff water increased with rate of biosolids application and decreased with time of postapplication on the two soils. The highest PO4(3-)-P and NH4+ -N concentrations, 4.96 and 97 mg L(-1), respectively, were recorded in the grassland soil treated with 90 Mg ha(-1) of biosolids 0.5 mo postapplication. For the same soil, rate, and postapplication age of biosolids, Cu exceeded the upper limit (0.50 mg L(-1) in drinking water for livestock. Ammonium N and PO4(3-)-P should be the main compounds considered when surface-applying biosolids. Ammonium N at concentrations found in all biosolids-treated plots may affect the quality of livestock drinking water by causing taste and smell problems. Orthophosphate can contribute to eutrophication if the runoff from biosolids-treated areas enter surface waters.     

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.     

A novel technique for the pre-concentration and extraction of inositol hexakisphosphate from soil extracts with determination by phosphorus-31 nuclear magnetic resonance

Inositol hexakisphosphate (IP6) is often the dominant form of soil organic phosphorus (P), but is rarely investigated because of the analytical difficulties encountered in its extraction, separation, and detection in environmental samples. In particular, recent advances in the study of soil organic P with 31P nuclear magnetic resonance (NMR) have been of limited use for the study of IP6, because the technique does not discriminate between IP6 and other forms of P. This was addressed by developing a novel analytical procedure using the retentive properties of gel-filtration gels for IP6, which allows the combined selective extraction and pre-concentration of IP6 from soil extracts with determination by 31P NMR. While the technique is still in the developmental stage, the results demonstrate that the gel does not interfere with 31P NMR analysis and retains IP6 to concentrations well above those required to give clear spectral signals. The technique has considerable potential for application to the study of IP6 in soil extracts and water samples and, with development, could help to answer fundamental questions regarding the dynamics of organic P in the environment.     

Fertilizer source effect on ground and surface water quality in drainage from turfgrass

Nutrients in surface and ground water can affect human and aquatic organisms that rely on water for consumption and habitat. A mass-balance field study was conducted over two years (July 2000-May 2001) to determine the effect of nutrient source on turfgrass runoff and leachate. Treatments were arranged in an incomplete randomized block design on a slope of 7 to 9% of Arkport sandy loam (coarseloamy, mixed, active, mesic Lamellic Hapludalf) and seeded with Kentucky bluegrass (Poa pratensis L.) and perennial ryegrass (Lolium perenne L.). Three natural organic (dairy and swine compost and a biosolid) and two synthetic organic nutrient sources (readily available urea and controlled-release N source sulfur-coated urea) were applied at rates of 50 and 100 kg N ha(-1) per application (200 kg ha(-1) yr(-1)). Runoff water collected from 33 storms and composite monthly leachate samples collected with ion exchange resins were analyzed for nitrate (NO3- -N), phosphate (PO4(3-) -P), and ammonium (NH4+ -N). Nutrient concentrations and losses in both runoff and leachate were highest for the 20-wk period following turfgrass seeding. The NO3- -N and NH4+ -N losses declined significantly once turfgrass cover was established, but PO4(3-) -P levels increased in Year 2. Turf's ability to reduce nutrient runoff and leachate was related to overall plant growth and shoot density. The use of natural organics resulted in greater P loss on a percent applied P basis, while the more soluble synthetic organics resulted in greater N loss.     

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

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

Phosphorus sorption and availability in soils amended with animal manures and sewage sludge

Soils that receive large applications of animal wastes and sewage sludge are vulnerable to releasing environmentally significant concentrations of dissolved P available to subsurface flow owing to the gradual saturation of the soil's P sorption capacity. This study evaluated P sorption (calculated from Langmuir isotherms) and availability of P (as CaCl2-P and resin P) in soils incubated for 20 d with poultry litter, poultry manure, cattle slurry, municipal sewage sludge, or KH2PO4, added on a P-equivalent basis (100 mg P kg(-1)). All the P sources had a marked negative effect on P sorption and a positive effect on P availability in all soils. In the cattle slurry- and KH2PO4-treated soils, the decreases in P sorption maximum (19-66%) and binding energy (25-89%) were consistently larger than the corresponding decreases (7-41% and 11-30%) in poultry litter-, poultry manure-, and sewage sludge-treated soils. The effects of cattle slurry and KH2PO4 on P availability were, in most cases, larger than those of the other P sources. In the poultry litter, poultry manure, and sewage sludge treatments, the increase in soil solution P was inversely related (R2 = 0.75) to the input of Ca from these relatively high Ca (13.5-42 g kg(-1)) sources. Correlation analyses implied that the magnitude of the changes in P sorption and availability was not related to the water-extractable P content of the P sources. Future research on the sustainable application of organic wastes to agricultural soils needs to consider the non-P- as well as P-containing components of the waste.     

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.     

A COMPARISON OF RUNOFF QUALITY EFFECTS OF ORGANIC AND INORGANIC FERTILIZERS APPLIED TO FESCUEGRASS PLOTS1

ABSTRACT: Application of fertilizer can degrade quality of runoff, particularly during the first post-application, runoff-producing storm. This experiment assessed and compared runoff quality impacts of organic and inorganic fertilizer application for a single simulated storm occurring seven days following application. The organic fertilizers used were poultry (Gallus gallus domesticus) litter, poultry manure, and swine (Sus scrofa domesticus) manure. All fertilizers were applied at an application rate of 217.6 kg N/ha. Simulated rainfall was applied at 50 mm/h for an average duration of 0.8 h. Runoff samples were collected, composited, and analyzed for nitrate N (NO₃-N), ammonia N (NH₃-N), total Kjeldahl N (TKN), ortho-P (PO₄-P), total P (TP), chemical oxygen demand (COD), total suspended solids (TSS), fecal coliforms (FC), and fecal streptococci (FS). Application of the fertilizers did not alter the hydrologic characteristics of the receiving plots relative to the control plots. Concentrations of fertilizer constituents were almost always greater from treated than from control plots and were usually much greater. Flow-weighted mean concentrations of NH₃-N, PO₄-P, and TP were highest for the inorganic fertilizer treatment (42.0, 26.6, and 27.9 mg/L, respectively). Runoff COD and TSS concentrations were greatest for the poultry litter treatment. Concentrations of FC and FS were greater for fertilized than for control plots with no differences among fertilized plots, but FC concentrations for all treatments were in excess of Arkansas' primary and secondary contact standards. Mass losses of fertilizer constituents were low (≤ 3 kg/ha) and were small proportions (≤ 3 percent) of amounts applied.     

Fourier transform infrared and fluorescence spectral features of organic matter in conventional and organic dairy manure

Organic dairy production has exhibited potential for growth in the United States dairy sector. However, little information is available on whether there is any difference in manure composition and quality between organic (OD) and conventional (CD) dairy manure even though the composition and quality are important parameters with respect to availability, utilization, and cycling of manure nutrients and environmental impact evaluation. We comparatively characterized whole and water-extracted materials of 15 OD and seven CD dairy manure samples by Fourier transform infrared (FT-IR) and fluorescence spectroscopies. Fourier transform infrared features of manure organic matter varied mainly in the 1650 to 1550 cm range, reflecting the presence of different N compounds in these manure samples. Fluorescence data revealed five fluorophore components present in the water-extracted organic matter from the manures. We found no clearly distinct value ranges in whole and water-extractable organic matter between the two types of dairy manure with respect to C and N contents and FT-IR and fluorescence spectral features. However, based on the average values, we observed general pattern differences on the effect of organic farming on the manure composition: OD contained less soluble C and N compounds on dry weight basis but more hydrophobic aliphatic groups in whole manure. The soluble organic matter in OD samples contained more stable humic- and lignin-related components and less amino/protein N-related components based on their spectroscopic features. These differences might be attributed to more forage feedstuffs in organic dairy farming management and more protein additives in conventional dairy feedstuffs. Information from this work may be useful in aiding organic dairy farmers in making manure management decisions.     

Nutrient load generated by storm event runoff from a golf course watershed

Turf, including home lawns, roadsides, golf courses, parks, etc., is often the most intensively managed land use in the urban landscape. Substantial inputs of fertilizers and water to maintain turf systems have led to a perception that turf systems are a major contributor to nonpoint source water pollution. The primary objective of this study was to quantify nutrient (NO(3)-N, NH(4)-N, and PO(4)-P) transport in storm-generated surface runoff from a golf course. Storm event samples were collected for 5 yr (1 Apr. 1998-31 Mar. 2003) from the Morris Williams Municipal Golf Course in Austin, TX. Inflow and outflow samples were collected from a stream that transected the golf course. One hundred fifteen runoff-producing precipitation events were measured. Median NO(3)-N and PO(4)-P concentrations at the outflow location were significantly (p < 0.05) greater than like concentrations measured at the inflow location; however, median outflow NH(4)-N concentration was significantly less than the median inflow concentration. Storm water runoff transported 1.2 kg NO(3)-N ha(-1) yr(-1), 0.23 kg NH(4)-N ha(-1) yr(-1), and 0.51 kg PO(4)-P ha(-1) yr(-1) from the course. These amounts represent approximately 3.3% of applied N and 6.2% of applied P over the contributing area for the same period. NO(3)-N transport in storm water runoff from this course does not pose a substantial environmental risk; however, the median PO(4)-P concentration exiting the course exceeded the USEPA recommendation of 0.1 mg L(-1) for streams not discharging into lakes. The PO(4)-P load measured in this study was comparable to soluble P rates measured from agricultural lands. The findings of this study emphasize the need to balance golf course fertility management with environmental risks, especially with respect to phosphorus.     

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.     

Inorganic nitrogen and phosphorus in Sierran forest O horizon leachate

High in situ concentrations of inorganic N and P have been reported in overland/litter interflow from Sierran forests, indicating that these nutrients are derived from the forest floor O horizons. To test this hypothesis, forest floor monoliths consisting of the combined O(e) and O(i) horizons were collected near the South Shore of Lake Tahoe, Nevada, for leaching experiments. Three monoliths were left intact, and three were hand-separated according to horizon for a total of three treatments (combined O(e)+O(i), O(e) only, and O(i) only) by three replications. Samples were randomized and placed into lined leaching bins. Initial leaching consisted of misting to simulate typical early fall precipitation. This was followed by daily snow applications and a final misting to simulate spring precipitation. Leachate was collected, analyzed for NH(4)(+)-N, NO(3)(-)-N, and PO(4)(3-)-P, and a nutrient balance was computed. There was a net retention of NH(4)(+)-N, but a net release of both NO(3)(-)-N and PO(4)(3-)-P, and a net release of inorganic N and P overall. Total contributions (mg) of N and P were highest from the O(e) and O(e)+O(i) combined treatments, but when expressed as per unit mass, significantly (p < 0.05) higher amounts of NO(3)(-)-N and PO(4)(3-)-P were derived from the O(i) materials. The nutrients in forest floor leachate are a potential source of biologically available N and P to adjacent surface waters. Transport of these nutrients from the terrestrial to the aquatic system in the Lake Tahoe basin may therefore play a part in the already deteriorating clarity of the lake.     

Preparation and FT-IR characterization of metal phytate compounds

Phytic acid (inositol hexaphosphoric acid, IP6) has long been recognized as the predominant organic P form in soil and animal manure. Whereas many studies have investigated the wet chemistry of IP6, there is little information on the characterization of solid metal IP6 compounds. This information is essential for further understanding and assessing the chemical behavior of IP6 in diverse soil-plant-water ecosystems. As the first step in full characterization, we synthesized eight metal phytate compounds and investigated their structural features using Fourier transform infrared spectroscopy (FT-IR). The absorption features from 900 to 1200 cm(-1) in FT-IR could be used to identify these phytates as: (i) light divalent metal (Ca and Mg) compounds with a sharp band and a broad band, (ii) heavy divalent metal (Cu and Mn) compounds with splitting broad bands, and (iii) trivalent metal (Al and Fe) compounds with a broad band and a shoulder band. Three different types of chemical structures of metal-phytate compounds were presented based on the FT-IR information. We further demonstrated that metal orthophosphates possessed different FT-IR spectral characteristics from their IP6 counterparts. The unique spectral features of metal phytates from 1000 to 700 cm(-1) could be used to distinguish phytate compounds from metal phosphate compounds. Thus, FT-IR analysis after fine tuning could provide an analytical tool to investigate the basic metal phytate chemistry in molecular levels, such as the competitive interactions between phosphate and phytate with a specific metal ion, and the conversion (or hydrolysis) of metal phytate to metal phosphate under various conditions.     

Effects of near-surface hydraulic gradients on nitrate and phosphorus losses in surface runoff

Phosphorous (P) and nitrogen (N) in runoff from agricultural fields are key components of nonpoint-source pollution and can accelerate eutrophication of surface waters. A laboratory study was designed to evaluate effects of near-surface hydraulic gradients on P and N losses in surface runoff from soil pans at 5% slope under simulated rainfall. Experimental treatments included three rates of fertilizer input (control [no fertilizer input], low [40 kg P ha(-1), 100 kg N ha(-1)], and high [80 kg P ha(-1), 200 kg N ha(-1)]) and four near-surface hydraulic gradients (free drainage [FD], saturation [Sa], artesian seepage without rain [Sp], and artesian seepage with rain [Sp + R]). Simulated rainfall of 50 mm h(-1) was applied for 90 min. The results showed that near-surface hydraulic gradients have dramatic effects on NO(3)-N and PO(4)-P losses and runoff water quality. Under the low fertilizer treatment, the average concentrations in surface runoff from FD, Sa, Sp, and Sp + R were 0.08, 2.20, 529.5, and 71.8 mg L(-1) for NO(3)-N and 0.11, 0.54, 0.91, and 0.72 mg L(-1) for PO(4)-P, respectively. Similar trends were observed for the concentrations of NO(3)-N and PO(4)-P under the high fertilizer treatment. The total NO(3)-N loss under the FD treatment was only 0.01% of the applied nitrogen, while under the Sp and Sp + R treatments, the total NO(3)-N loss was 11 to 16% of the applied nitrogen. These results show that artesian seepage could make a significant contribution to water quality problems.     

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.     

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.     

Use of drinking water treatment residuals as a potential best management practice to reduce phosphorus risk index scores

The P risk index system has been developed to identify agricultural fields vulnerable to P loss as a step toward protecting surface water. Because of their high Langmuir phosphorus adsorption maxima (P(max)), use of drinking water treatment residuals (WTRs) should be considered as a best management practice (BMP) to lower P risk index scores. This work discusses three WTR application methods that can be used to reduce P risk scores: (i) enhanced buffer strip, (ii) incorporation into a high soil test phosphorus (STP) soil, and (iii) co-blending with manure or biosolids. The relationship between WTR P(max) and reduction in P extractability and runoff P was investigated. In a simulated rainfall experiment, using a buffer strip enhanced with 20 Mg WTR ha(-1), runoff P was reduced by from 66.8 to 86.2% and reductions were related to the WTR P(max). When 25 g kg(-1) WTR was incorporated into a high STP soil of 315 mg kg(-1) determined using Mehlich-3 extraction, 0.01 M calcium chloride-extractable phosphorus (CaCl(2)-P) reductions ranged from 60.9 to 96.0% and were strongly (P < 0.01) related to WTR P(max). At a 100 g kg(-1) WTR addition, Mehlich 3-extractable P reductions ranged from 41.1 to 86.7% and were strongly (P < 0.01) related to WTR P(max). Co-blending WTR at 250 g kg(-1) to manure or biosolids reduced CaCl(2)-P by >75%. The WTR P(max) normalized across WTR application rates (P(max) x WTR application) was significantly related to reductions in CaCl(2)-P or STP. Using WTR as a P risk index modifying factor will promote effective use of WTR as a BMP to reduce P loss from agricultural land.     

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

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