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.     

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

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

What aspect of dietary modification in broilers controls litter water-soluble phosphorus: dietary phosphorus, phytase, or calcium?

Environmental concerns about phosphorus (P) losses from animal agriculture have led to interest in dietary strategies to reduce the concentration and solubility of P in manures and litters. To address the effects of dietary available phosphorus (AvP), calcium (Ca), and phytase on P excretion in broilers, 18 dietary treatments were applied in a randomized complete block design to each of four replicate pens of 28 broilers from 18 to 42 d of age. Treatments consisted of three levels of AvP (3.5, 3.0, and 2.5 g kg(-1)) combined with three levels of Ca (8.0, 6.9, and 5.7 g kg(-1)) and two levels of phytase (0 and 600 phytase units [FTU]). Phytase was added at the expense of 1.0 g kg(-1) P from dicalcium phosphate. Fresh litter was collected from pens when the broilers were 41 d of age and analyzed for total P, soluble P, and phytate P as well as P composition by (31)P nuclear magnetic resonance (NMR) spectroscopy. Results indicated that the inclusion of phytase at the expense of inorganic P or reductions in AvP decreased litter total P by 28 to 43%. Litter water-soluble P (WSP) decreased by up to 73% with an increasing dietary Ca/AvP ratio, irrespective of phytase addition. The ratio of WSP/total P in litter decreased as the dietary Ca/AvP ratio increased and was greater in the phytase-amended diets. This study indicated that while feeding reduced AvP diets with phytase decreased litter total P, the ratio of Ca/AvP in the diet was primarily responsible for effects on WSP. This is important from an environmental perspective as the amount of WSP in litter could be related to potential for off-site P losses following land application of litter.     

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

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

Phosphorus 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.     

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.     

Diet modification to reduce phosphorus surpluses: a mass balance approach

Diet modification to reduce phosphorus (P) concentrations in manures has been developed in response to environmental concerns over P losses from animal agriculture to surface waters. We used USDA-NASS statistics on animal numbers and crop production to calculate county scale mass balances for manure P production, P removed in harvested portion of crops, and the potential effects of diet modification. Although spreading manure evenly over all crop acreage within a county is unlikely to occur, these calculations give a good indication as to the impact diet modification to reduce P can have at a regional or national scale. There was a high degree of regional variability in manure P surpluses (e.g., with the large crop acreages in the grain belt leading to large P offtake in crops preventing most P surpluses). In 89% of counties, there was a deficit of manure P relative to crop P removal; therefore there was a manure P surplus in 11% of counties. Diet modification decreased the percentage of states with a manure P surplus from 11 to 8%, a decrease of approximately 27%. Diet modification decreased the percentage of counties with the greatest surpluses of manure P (>30 kg ha(-1)) from 3% of all counties to 1%. Diet modification to decrease manure P is an important part of strategies to alleviate environmental concerns associated with surplus manure P in many areas, but additional strategies to deal with manure P surpluses are needed in some areas.     

Plant nutrient issues for sustainable land application

Interest in plant nutrient issues for sustainable land application of residuals is increasingly driven by environmental concerns. The indicators of concern are P and N in surface waters, nitrate leaching, and emissions of ammonia and greenhouse gases. Federal regulations require residual application rates to be on a N basis at most, and on a P basis when risk of P loss in surface runoff is high. Modeling of mineralization offers the potential for more accurate determinations of potentially available nitrogen (PAN) and quick tests could allow the determination of PAN on residuals immediately before land application. Methods for reducing ammonia emissions from livestock operations and new techniques for quantifying emissions under field conditions are being developed. Calibration and validation of P loss assessment tools is an ongoing concern and the interpretation of edge of field P losses warrants further attention. The solubility of P in residuals and soils can be influenced by various amendments or treatment processes. High available P grains or phytase enzyme supplementation can reduce total and soluble P in animal manures by reducing the need for diet supplementation with inorganic P. The use of synchrotron-based X-ray absorption spectroscopy has identified chemical forms of inorganic P. Considerable progress has been made addressing plant nutrient issues for sustainable land application and interest in this topic will remain strong into the foreseeable future.     

Emerging technologies for removing nonpoint phosphorus from surface water and groundwater: introduction

Coastal and freshwater eutrophication continues to accelerate at sites around the world despite intense efforts to control agricultural P loss using traditional conservation and nutrient management strategies. To achieve required reductions in nonpoint P over the next decade, new tools will be needed to address P transfers from soils and applied P sources. Innovative remediation practices are being developed to remove nonpoint P sources from surface water and groundwater using P sorbing materials (PSMs) derived from natural, synthetic, and industrial sources. A wide array of technologies has been conceived, ranging from amendments that immobilize P in soils and manures to filters that remove P from agricultural drainage waters. This collection of papers summarizes theoretical modeling, laboratory, field, and economic assessments of P removal technologies. Modeling and laboratory studies demonstrate the importance of evaluating P removal technologies under controlled conditions before field deployment, and field studies highlight several challenges to P removal that may be unanticipated in the laboratory, including limited P retention by filters during storms, as well as clogging of filters due to sedimentation. Despite the potential of P removal technologies to improve water quality, gaps in our knowledge remain, and additional studies are needed to characterize the long-term performance of these technologies, as well as to more fully understand their costs and benefits in the context of whole-farm- and watershed-scale P management.     

Liming poultry manures to decrease soluble phosphorus and suppress the bacteria population

Stabilizing phosphorus (P) in poultry waste to reduce P losses from manured soils is important to protect surface waters, while pathogens in manures are an emerging issue. This study was conducted to evaluate CaO and Ca(OH)2 for killing manure bacterial populations (pathogens) and stabilizing P in poultry wastes and to investigate the influence on soils following amendment with the treated wastes. Layer manure and broiler litter varying in moisture content were treated with CaO and Ca(OH)2 at rates of 2.5, 5, 10, and 15% by weight. All treated wastes were analyzed for microbial plate counts, pH, and water-soluble phosphorus (WSP), while a few selected layer manures were analyzed by phosphorus X-ray absorption near edge structure (XANES). A loamy sand and a silt loam were amended with broiler litter and layer manure treated with CaO at rates of 0, 2.5, 5, 10, and 15% and soil WSP and pH were measured at times 1, 8, and 29 d. Liming reduced bacterial populations, with greater rates of lime leading to greater reductions; for example 10% CaO applied to 20% solids broiler litter reduced the plate counts from 793,000 to 6500 mL-1. Liming also reduced the WSP in the manures by over 90% in all cases where at least 10% CaO was added. Liming the manures also reduced WSP in soils immediately following application and raised soil pH. The liming process used successfully reduced plate counts and concerns about P losses in runoff following land application of these limed products due to decreased WSP.     

Occurrence of antimicrobials in animal manure-amended soils around the breeding farms: The case of the Saigon River (southern Vietnam)

The excessive use of antimicrobials in animal rearing and the associated environmental hazards have become a pressing issue. Animal agriculture is often viewed as a significant contributor to environmental degradation due to the residues of antimicrobials. It is a common practice to use livestock waste as a soil enhancer in farming. Despite some research into antimicrobials, there is room for more comprehensive data regarding these pollutants in animal farming environments. A handful of earlier studies have identified antimicrobials in animal waste. This research undertook the task of examining and evaluating soils amended with animal waste (from chickens, cows, and pigs) for the presence of seven specific antimicrobials. The antimicrobials under scrutiny included trimethoprim (TRI), ormethoprim (ORM), ofloxacin (OFL), norfloxacin (NOR), tetracycline (TET), chlortetracycline (CTE), and tylosin (TLS). Soil samples were collected from areas surrounding breeding farms located upstream of the Sai Gon River. These samples were then subjected to laboratory analysis, which involved solid-phase extraction using ultrasonic waves and the application of high-performance liquid chromatography-tandem mass spectrometry (LCMS/MS) to identify the antimicrobials. TRI, which had the highest average concentration (2.603–91.304 μg/kg), and OFL, with the second highest average concentration (1.815–15.832 μg/kg), were detected in all soil samples amended with manure. CTE, with the third highest average concentration, was found in soils amended with cow and pig waste (1.625–15.486 μg/kg). ORM and TE, with lower average concentrations (0.595–1.318 μ and 11.537–13.569 μg/kg, respectively), were only detected in soils amended with chicken waste, while NOR was only found in soils amended with cow waste. These findings indicate that the use of antimicrobials in animal farming can negatively impact the soil ecosystem. Consequently, these results can contribute to the creation of guidelines for monitoring antimicrobial residues in agricultural ecosystems.     

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.     

Phosphorus release from a manure-impacted spodosol: effects of a water treatment residual

Long-term depositions of animal manures affect P dynamics in soils and can pose environmental risks associated with P losses. Laboratory studies were done on P solubility characteristics in a manure-impacted Immokalee soil (sandy, siliceous, hyperthermic Arenic Alaquod) and the effectiveness of water treatment residual (WTR) in controlling P leaching. Soil samples with contrasting initial total P concentrations were prepared by mixing samples of a manure-impacted surface A horizon and a minimally P-impacted E horizon. Effects of mixing various ratios of A and E horizons, WTR rates (0, 25, 50, and 100 g kg(-1)), and depths of WTR incorporation (mixed throughout the soil column or partially incorporated) on P leaching were determined. Between 62 and 77% of total P was released from the soil mixes by successive water extractions, suggesting a considerable buffering capacity of this manure-impacted soil to resupply P into solution. Between 224 and 408 mg kg(-1) P were leached during the 36-wk leaching period in the absence of WTR. Mixing WTRs with soil reduced soluble P concentration in leachates by as much as 99.8% compared with samples without WTR. Thoroughly mixing WTR with the entire soil column (15 cm) was much more efficient than mixing WTR with only the top 7.5 cm of soil. Calcium- and Mg-P forms appear to control P release in soils without WTR, whereas sorption-desorption reactions probably determine P leaching in WTR-treated samples. Soil P distribution in various chemical forms was affected by WTR additions. Data suggest that WTR-immobilized P is stable in the long term.     

Phosphorus restrictions for land application of biosolids: current status and future trends

The application of biosolids (sewage sludge) to agricultural soils provides P in excess of crop needs when applied to meet the N needs of most agronomic crops. These overapplications can result in the buildup of P in soils to values well above those needed for optimum crop yields and also may increase risk of P losses to surface and ground waters. Because of concerns regarding the influence of P on water quality in the USA, many state and federal agencies now recommend or require P-based nutrient management plans for animal manures. Similar actions are now under consideration for the land application of biosolids. We reviewed the literature on this subject and conducted a national survey to determine if states had restrictions on P levels in biosolids-amended soils. The literature review indicates that while the current N-based approach to biosolids management does result in increases of soil P, some properties of biosolids may mitigate the environmental risk to water quality associated with land application of P in biosolids. Results of the survey showed that 24 states have regulations or guidelines that can be imposed to restrict land application of biosolids based on P. Many of these states use numerical thresholds for P in biosolids-amended soils that are based on soil test phosphorus (STP) values that are much greater than the values considered to be agronomically beneficial. We suggest there is the need for a comprehensive environmental risk assessment of biosolids P. If risk assessment suggests the need for regulation of biosolids application, we suggest regulations be based on the P Site Index (PSI), which is the method being used by most states for animal manure management.     

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.     

The phosphorus footprint of China's food chain: implications for food security, natural resource management, and environmental quality

Efficient use of phosphorus (P) for producing food, preventing water pollution, and managing a dwindling rock P reserve are major challenges for China. We analyzed P stocks and flows in the Chinese food chain to identify where P use efficiency can be improved, where P leaks to the environment, and the research, technologies, and policies needed to improve P use. We found a high degree of inefficiency; of 6652 Gg P entering the food chain, only 1102 Gg P (18%) exit as food for humans. The greatest inefficiencies were a large build-up of soil P (3670 Gg P yr; 52% of P inputs) and high P losses to the environment from animal production (1582 Gg P yr; 60% of excreted P). Improving P use in China must focus on national-scale nutrient management strategies, better animal nutrition, and adoption of technologies and policies to reduce P discharges from the animal sector and recycle P as manures in agriculture.     

Phosphorus runoff from agricultural land and direct fertilizer effects: a review

Phosphorus (P) is one of the most important mineral nutrients in agricultural systems, and along with nitrogen (N), is generally the most limiting nutrient for plant production. Farming systems have intensified greatly over time, and in recent years it has become apparent that the concomitant increase in losses of N and P from agricultural land is having a serious detrimental effect on water quality and the environment. The last two decades have seen a marked increase in research into the issues surrounding diffuse losses of P to surface and ground water. This paper reviews this research, examining the issue of P forms in runoff, and highlighting the exceptions to some generally held assumptions about land use and P transport. In particular the review focuses on P losses associated with recent P fertilizer application, as opposed to organic manures, both on the amounts and the forms of P in runoff water. The effects of the physicochemical characteristics of different forms of P fertilizer are explored, particularly in relation to water solubility. Various means of mitigating the risk of loss of P are discussed. It is argued that the influence of recent fertilizer applications is an under-researched area, yet may offer the most readily applicable opportunity to mitigate P losses by land users. This review highlights and discusses some options that have recently become available that may make a significant contribution to the task of sustainable management of nutrient losses from agriculture.     

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.     

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.     

Evaluation of phosphorus transport in surface runoff from packed soil boxes

Evaluation of phosphorus (P) management strategies to protect water quality has largely relied on research using simulated rainfall to generate runoff from either field plots or shallow boxes packed with soil. Runoff from unmanured, grassed field plots (1 m wide x 2 m long, 3-8% slope) and bare soil boxes (0.2 m wide and 1 m long, 3% slope) was compared using rainfall simulation (75 mm h(-1)) standardized by 30-min runoff duration (rainfall averaged 55 mm for field plots and 41 mm for packed boxes). Packed boxes had lower infiltration (1.2 cm) and greater runoff (2.9 cm) and erosion (542 kg ha(-1)) than field plots (3.7 cm infiltration; 1.8 cm runoff; 149 kg ha(-1) erosion), yielding greater total phosphorus (TP) losses in runoff. Despite these differences, regressions of dissolved reactive phosphorus (DRP) in runoff and Mehlich-3 soil P were consistent between field plots and packed boxes reflecting similar buffering by soils and sediments. A second experiment compared manured boxes of 5- and 25-cm depths to determine if variable hydrology based on box depth influenced P transport. Runoff properties did not differ significantly between box depths before or after broadcasting dairy, poultry, or swine manure (100 kg TP ha(-1)). Water-extractable phosphorus (WEP) from manures dominated runoff P, and translocation of manure P into soil was consistent between box types. This study reveals the practical, but limited, comparability of field plot and soil box data, highlighting soil and sediment buffering in unamended soils and manure WEP in amended soils as dominant controls of DRP transport.