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.     

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.     

Sediment phosphorus extractants for phosphorus-31 nuclear magnetic resonance analysis: a quantitative evaluation

The influence of pre-extractant, extractant, and post-extractant on total extracted amounts of P and organic P compound groups measured with 31P nuclear magnetic resonance (31P-NMR) in lacustrine sediment was examined. The main extractants investigated were sodium hydroxide (NaOH) and sodium hydroxide ethylenediaminetetraacetic acid (NaOH-EDTA) with bicarbonate buffered dithionite (BD) or EDTA as pre-extractants. Post extractions were conducted using either NaOH or NaOH-EDTA, depending on the main extractant. Results showed that the most efficient combination of extractants for total P yield was NaOH with EDTA as pre-extractant, yielding almost 50% more than the second best procedure. The P compound groups varying the most between the different extraction procedures were polyphosphates and pyrophosphates. NaOH with BD as pre-extractant was the most efficient combination for these compound groups.     

How accurate is the assessment of phosphorus pools in poultry litter by sequential extraction?

Amending poultry litter with Al sulfate (alum) has proven effective in reducing water-soluble P in the litter and in runoff from fields that have received litter applications. Although its effectiveness has been demonstrated on a macroscopic scale in the field or in the poultry houses, little is known about P speciation in either alum-amended or unamended litter. This knowledge is important for the evaluation of long-term stability and bioavailability of P, which is a necessary prerequisite for the assessment of the sustainability of intensive poultry operations. Here we report results from an investigation of alum-amended poultry litter (PL) that combined a chemical extraction sequence with solid-state 31P nuclear magnetic resonance (NMR) spectroscopic analysis of the residues. Aluminum is predominantly found in the fine size separate (<125 microm), indicating that the alum added to the poultry houses hydrolyzed without being completely dispersed in the litter. The NMR spectra confirmed the hypothesis that calcium phosphate phases are only dissolved during extraction with dilute acid and phosphate associated with Al is mainly dissolved during extraction with NaOH. Extraction of phosphate associated with Al was incomplete, however, as evidenced by 31P NMR spectroscopy. It could also be demonstrated that the extraction sequence overestimates the calcium phosphate fraction by an order of magnitude in this particular sample. Results from sequential chemical extraction should therefore be used with caution when assessing the magnitude of different phosphate pools in poultry litter.     

The impact of alum addition on organic P transformations in poultry litter and litter-amended soil

Poultry litter treatment with alum (Al(2)(SO(4))(3) . 18H(2)O) lowers litter phosphorus (P) solubility and therefore can lower litter P release to runoff after land application. Lower P solubility in litter is generally attributed to aluminum-phosphate complex formation. However, recent studies suggest that alum additions to poultry litter may influence organic P mineralization. Therefore, alum-treated and untreated litters were incubated for 93 d to assess organic P transformations during simulated storage. A 62-d soil incubation was also conducted to determine the fate of incorporated litter organic P, which included alum-treated litter, untreated litter, KH(2)PO(4) applied at 60 mg P kg(-1) of soil, and an unamended control. Liquid-state (31)P nuclear magnetic resonance indicated that phytic acid was the only organic P compound present, accounting for 50 and 45% of the total P in untreated and alum-treated litters, respectively, before incubation and declined to 9 and 37% after 93 d of storage-simulating incubation. Sequential fractionation of litters showed that alum addition to litter transformed 30% of the organic P from the 1.0 mol L(-1) HCl to the 0.1 mol L(-1) NaOH extractable fraction and that both organic P fractions were more persistent in alum-treated litter compared with untreated litter. The soil incubation revealed that 0.1 mol L(-1) NaOH-extractable organic P was more recalcitrant after mixing than was the 1.0 mol L(-1) HCl-extractable organic P. Thus, adding alum to litter inhibits organic P mineralization during storage and promotes the formation of alkaline extractable organic P that sustains lower P solubility in the soil environment.     

Chemical extraction methods to assess bioavailable arsenic in soil and solid media

Soil ingestion by children is an important pathway in assessing public health risks associated with exposure to arsenic-contaminated soils. Soil chemical methods are available to extract various pools of soil arsenic, but their ability to measure bioavailable arsenic from soil ingestion is unknown. Arsenic extracted by five commonly used soil extractants was compared with bioavailable arsenic measured in vivo by immature swine (Sus scrofa) dosing trials. Fifteen contaminated soils that contained 233 to 17 500 mg kg(-1) arsenic were studied. Soil extractants were selected to dissolve surficially adsorbed and/or readily soluble arsenic (water, 1 M sodium acetate, 0.1 M Na2HPO4/0.1 M NaH2PO4) and arsenic in Fe and Mn oxide minerals (hydroxylamine hydrochloride, ammonium oxalate). The mean percent of total arsenic extracted was: ammonium oxalate (53.6%) > or = hydroxylamine hydrochloride (51.7%) > phosphate (10.5%), acetate (7.16%) > water (0.15%). The strongest relationship between arsenic determined by soil chemical extraction and in vivo bioavailable arsenic was found for hydroxylamine hydrochloride extractant (r = 0.88, significant at the 0.01 probability level). Comparison of the amount of arsenic extracted by soil methods with bioavailable arsenic showed the following trend: ammonium oxalate, hydroxylamine hydrochloride > in vivo > phosphate, acetate > water. The amount of arsenic dissolved in the stomach (potentially bioavailable) is between surficially adsorbed (extracted by phosphate or acetate) and surficially adsorbed + nonsurficial forms in Fe and Mn oxides (extracted by hydroxylamine hydrochloride or ammonium oxalate). Soil extraction methods that dissolve some of the amorphous Fe, such as hydroxylamine hydrochloride, can be designed to provide closer estimates of bioavailable arsenic.     

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.     

Soil testing to predict phosphorus leaching

Subsurface pathways can play an important role in agricultural phosphorus (P) losses that can decrease surface water quality. This study evaluated agronomic and environmental soil tests for predicting P losses in water leaching from undisturbed soils. Intact soil columns were collected for five soil types that a wide range in soil test P. The columns were leached with deionized water, the leachate analyzed for dissolved reactive phosphorus (DRP), and the soils analyzed for water-soluble phosphorus (WSP), 0.01 M CaCl2 P (CaCl2-P), iron-strip phosphorus (FeO-P), and Mehlich-1 and Mehlich-3 extractable P, Al, and Fe. The Mehlich-3 P saturation ratio (M3-PSR) was calculated as the molar ratio of Mehlich-3 extractable P/[Al + Fe]. Leachate DRP was frequently above concentrations associated with eutrophication. For the relationship between DRP in leachate and all of the soil tests used, a change point was determined, below which leachate DRP increased slowly per unit increase in soil test P, and above which leachate DRP increased rapidly. Environmental soil tests (WSP, CaCl2-P, and FeO-P) were slightly better at predicting leachate DRP than agronomic soil tests (Mehlich-1 P, Mehlich-3 P, and the M3-PSR), although the M3-PSR was as good as the environmental soil tests if two outliers were omitted. Our results support the development of Mehlich-3 P and M3-PSR categories for profitable agriculture and environmental protection; however, to most accurately characterize the risk of P loss from soil to water by leaching, soil P testing must be fully integrated with other site properties and P management practices.     

Long-term effects of poultry litter, alum-treated litter, and ammonium nitrate on phosphorus availability in soils

Alum (Al2(SO4)(3).14H2O) additions to poultry litter result in lower ammonia (NH3) volatilization and phosphorus (P) runoff; however, the long-term effects of alum on soil P behavior have been unknown. The objectives of this study were to evaluate the long-term effects of poultry litter, alum-treated litter, and ammonium nitrate (NH4NO3) on P availability in soils and P runoff. Two studies were initiated in 1995: a small plot (1.5x3.0 m) study and a paired watershed (0.405 ha) study. In the small plot study 13 treatments (control, four rates of normal litter, four rates of alum-treated litter, and four rates of NH4NO3) were applied to tall fescue (Festuca arundinacea Schreb.) plots. Results show that after 7 yr water-extractable P (WEP) in surface soil samples was greater with normal litter, but Mehlich III P was greater in surface soils fertilized with alum-treated litter. When soil samples were taken at depth intervals to 50 cm in Year 7, Mehlich III P was only greater in the surface 5 cm for soils fertilized with alum-treated litter. At lower depths Mehlich III P was greater with normal litter, and WEP was up to 288% greater when normal litter was used, indicating that alum significantly reduced P leaching. Uptake of P by fescue was not affected by alum. Results from the paired watershed study showed P loss in runoff was 340% greater for normal litter than for alum-treated litter. This research, combined with earlier work that shows alum use improves air and soil quality, supports the use of alum as a long-term solution to reducing P runoff and leaching.     

Broiler diet modification and litter storage: impacts on phosphorus in litters, soils, and runoff

Modifying broiler diets to mitigate water quality concerns linked to excess phosphorus (P) in regions of intensive broiler production has recently increased. Our goals were to evaluate the effects of dietary modification, using phytase and reduced non-phytate phosphorus (NPP) supplementation, on P speciation in broiler litters, changes in litter P forms during long-term storage, and subsequent impacts of diets on P in runoff from litter-amended soils. Four diets containing two levels of NPP with and without phytase were fed to broilers in a three-flock floor pen study. After removal of the third flock, litters were stored for 440 d at their initial moisture content (MC; 24%) and at a MC of 40%. Litter P fractions and orthophosphate and phytate P concentrations were determined before and after storage. After storage, litters were incorporated with a sandy and silt loam and simulated rainfall was applied. Phytase and reduced dietary NPP significantly reduced litter total P. Reducing dietary NPP decreased water-extractable inorganic phosphorus (IP) and the addition of dietary phytase reduced NaOH- and HCl-extractable organic P in litter, which correlated well with orthophosphate and phytic acid measured by 31P nuclear magnetic resonance (NMR), respectively. Although dry storage caused little change in P speciation, wet storage increased concentrations of water-soluble IP, which increased reactive P in runoff from litter-amended soils. Therefore, diet modification with phytase and reduced NPP could be effective in reducing P additions on a watershed scale. Moreover, efforts to minimize litter MC during storage may reduce the potential for dissolved P losses in runoff.     

Optimal conditions of Al and Fe extraction from laterite soil using D-optimal design

This paper reports pioneering work in identifying an alternative coagulation agent of wastewater treatment, given the availability of commonly used agents are of a higher cost relative to more natural sources, such as soil. The alternative proposed is laterite soil from northern Malaysia because it contains high amounts of Al and Fe, which are well-known coagulants. The soil was grinded and sieved to obtain uniform particle sizes of <250???m. Al and Fe were extracted from the soil. Extraction agents: (1) HCl, (2) NaOH, and (3) HCl?+?NaCl were chosen. It was found that the most effective agent to extract Fe was 5?N HCl while to extract Al was HCl?+?NaCl, 2 and 4?N, respectively. D-optimal design observed that extraction time t, temperature T, and ratio of amount of laterite soil to amount of extractants r, showed a significant effect on Al extraction. In contrast, the combination of factors t and r exhibited insignificant effect on Fe extraction while other factors were significant. The optimum conditions for extraction of both Al and Fe were 90?°C, 40?min, for r?=?1:15, which gave [Fe]?=?1,870?mg/l and [Al]?=?0.17?mg/l and 90?°C, 90?min, for r?=?1:10, which gave [Fe]?=?2,900?mg/l and [Al]?=?0.130?mg/l. Since concentration of Fe extracted from laterite soil was high, it was concluded that laterite soil can be considered as an alternative and novel source of coagulant applicable in a wastewater treatment coagulation process.     

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

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

Phosphorus in fresh and dry dung of grazing dairy cattle, deer, and sheep: sequential fraction and phosphorus-31 nuclear magnetic resonance analyses

Knowledge of phosphorus (P) fractions in dung of animals (dairy cattle, deer, sheep) grazing pasture is important for soil fertility and the potential for P transport in runoff and subsequent surface water quality deterioration. We used sequential fractionation and 31P nuclear magnetic resonance (NMR) spectroscopy to determine P forms in fresh and air-dried (to simulate field conditions during grazing) dung. Sheep dung was richest in P (8 g kg(-1)), and cattle dung poorest (5.5 g kg(-1)). Data for sequential fractionation indicated that most P was extractable by water (15-36%) and bicarbonate (36-45%) in fresh dung, and shifted toward recalcitrant, HCl (12-28%), and residual P forms (15-31%) with drying. Organic P concentration in dung was poor (maximum of 15% of total P), probably due to the poor concentration of phytate in pasture. The 31P NMR spectra of NaOH-EDTA extracts supported this by detecting a low concentration of monoesters (9-19% of total P in extracts), of which phytate is a major component. The 31P NMR data also showed that changes in organic P concentration with drying could be due to the degradation of diesters. Data indicate the decreasing bioavailability of dairy cattle, deer, and sheep dung with drying and the need to consider this effect with respect to P returns for soil fertility and the potential for runoff.     

Relationship between soil test phosphorus and phosphorus in runoff: effects of soil series variability

Phosphorus loss in runoff from agricultural fields has been identified as an important contributor to eutrophication. The objective of this research was to determine the relationship between phosphorus (P) in runoff from a benchmark soil (Cecil sandy loam; fine, kaolinitic, thermic Typic Kanhapludult) and Mehlich III-, deionized water-, and Fe(2)O(3)-extractable soil P, and degree of phosphorus saturation (DPS). Additionally, the value of including other soil properties in P loss prediction equations was evaluated. Simulated rainfall was applied (75 mm h(-1)) to 54 1-m(2) plots installed on six fields with different soil test phosphorus (STP) levels. Runoff was collected in its entirety for 30 min and analyzed for total P and dissolved reactive phosphorus (DRP). Soil samples were collected from 0- to 2-, 0- to 5-, and 0- to 10-cm depths. The strongest correlation for total P and DRP occurred with DPS (r(2) = 0.72). Normalizing DRP by runoff depth resulted in improved correlation with deionized water-extractable P for the 0- to 10-cm sampling depth (r(2) = 0.81). The STP levels were not different among sampling depths and analysis of the regression equations revealed that soil sampling depth had no effect on the relationship between STP and P in runoff. For all forms of P in runoff and STP measures, the relationship between STP and runoff P was much stronger when the data were split into groups based on the ratio of oxalate-extractable Fe to Al. For all forms of P in runoff and all STP methods, R(2) increased with the inclusion of oxalate-extractable Al and Fe in the regression equation. The results of this study indicate that inclusion of site-specific information about soil Al and Fe content can improve the relationship between STP and runoff P.     

Stray field nuclear magnetic resonance of soil water: development of a new, large probe and preliminary results

Development, characterization, and preliminary results of a recent technique capable of local measurements of pore-size distribution by a spatially resolved low resolution nuclear magnetic resonance (NMR) technique are described. Potential environmental uses include studying the change in pore-size distribution caused by surface compaction, which influences surface runoff, and obtaining information on the physical state of non-aqueous compounds in porous materials, which should aid the selection of appropriate soil remediation methods. Stray field (STRAFI) imaging is an NMR technique that allows distortion-free imaging of materials with short NMR relaxation times. The sample is placed in the strong axial fringe field gradient of a superconducting NMR magnet. We report on a new, unique, large 5-cm-diameter STRAFI probe, and its use for three preliminary test cases: water in ceramics of known pore size, paraffin wax and oil in sandstone rock, and water in soil at different matric potentials. The imaging is confined to one dimension with a spatial resolution of the order of 100 microm for protons. The optimum position for imaging occurs at 2.62 T and a gradient of 12.1 T/m. Water relaxation decay curves can be measured at any position in the 8-cm-long sample. These curves are decomposed into a series of terms each corresponding to a different pore size. Preliminary results show continuum fits to decay curves for a soil drained to three different matric potentials. Such information will be useful for interpreting water retention curves and will lead to understanding of the behavior of fluids in the vadose zone.     

Broiler litter as a micronutrient source for cotton: concentrations in plant parts

Analytically, poultry litter contains nearly all essential micronutrients but the extent of phytoavailability of these nutrients and whether cotton (Gossypium hirsutum L.) and other crop plants can receive adequate amounts of these nutrients from litter is not fully known. The objective of this research was to determine whether cotton receives sufficient amounts of Fe, Cu, Mn, and Zn from litter and estimate the efficiency of cotton in extracting these metal nutrients from litter in the absence of any other source of the micronutrients. The greenhouse research used plastic pots filled with approximately 11 kg of a 2:1 (v/v) sand to vermiculite growing mix. Cotton (cv. Stoneville 474) was grown in the pots fertilized with broiler litter at rates of 30, 60, 90, or 120 g pot(-1) in a factorial combination with four supplemental nutrient solution (NS) treatments. The nutrient solutions consisted of full Hoagland's nutrient solution (NS-full); a solution of the macronutrients N, P, K, Ca, and Mg (NS-macro); a solution of the micronutrients Fe, Zn, Mn, Cu, B, and Mo (NS-micro); and water (NS-none). Based on tissue nutrient analysis, a one-time broiler litter application supplied adequate amounts of Fe, Cu, and Mn to bring the concentration of these nutrients in upper leaves within published sufficiency ranges. Zinc, with <17 mg kg(-1) concentration in the upper leaves, was the only micronutrient below the established sufficiency range regardless of the rate of applied litter. Cotton extracted Fe and Mn more efficiently than Cu or Zn, removing as much as 8.8% of Fe and 7.2% of Mn supplied by 30 g litter pot(-1). In contrast, the extraction efficiency was 1.7% for Cu and 1.9% for Zn. Roots accumulated 58% of the total absorbed Fe and 64% of Cu, and leaves accumulated 32% of the Fe and only 13% of the Cu supplied by litter. In contrast, only 16% of the total absorbed Mn and 23% of Zn accumulated in roots while leaves accumulated 64% of the total Mn and 37% of Zn. These results demonstrate that broiler litter is a valuable source of the metal nutrients supplying Fe, Cu, and Mn in full and Zn in part, but a very large fraction of the litter-supplied metal nutrients remained in the growing mix.     

Evaluation of phosphorus characterization in broiler ileal digesta, manure, and litter samples: (31)P-NMR vs. HPLC

Using 31-phosphorus nuclear magnetic resonance spectroscopy ((31)P-NMR) to characterize phosphorus (P) in animal manures and litter has become a popular technique in the area of nutrient management. To date, there has been no published work evaluating P quantification in manure/litter samples with (31)P-NMR compared to other accepted methods such as high performance liquid chromatography (HPLC). To evaluate the use of (31)P-NMR to quantify myo-inositol hexakisphosphate (phytate) in ileal digesta, manure, and litter from broilers, we compared results obtained from both (31)P-NMR and a more traditional HPLC method. The quantification of phytate in all samples was very consistent between the two methods, with linear regressions having slopes ranging from 0.94 to 1.07 and r(2) values of 0.84 to 0.98. We compared the concentration of total monoester P determined with (31)P-NMR with the total inositol P content determined with HPLC and found a strong linear relationship between the two measurements having slopes ranging from 0.91 to 1.08 and r(2) values of 0.73 to 0.95. This suggests that (31)P-NMR is a very reliable method for quantifying P compounds in manure/litter samples.     

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.     

Relating soil phosphorus to dissolved phosphorus in runoff: a single extraction coefficient for water quality modeling

Phosphorus transport from agricultural soils contributes to eutrophication of fresh waters. Computer modeling can help identify agricultural areas with high potential P transport. Most models use a constant extraction coefficient (i.e., the slope of the linear regression between filterable reactive phosphorus [FRP] in runoff and soil P) to predict dissolved P release from soil to runoff, yet it is unclear how variations in soil properties, management practices, or hydrology affect extraction coefficients. We investigated published data from 17 studies that determined extraction coefficients using Mehlich-3 or Bray-1 soil P (mg kg(-1)), water-extractable soil P (mg kg(-1)), or soil P sorption saturation (%) as determined by ammonium oxalate extraction. Studies represented 31 soils with a variety of management conditions. Extraction coefficients from Mehlich-3 or Bray-1 soil P were not significantly different for 26 of 31 soils, with values ranging from 1.2 to 3.0. Extraction coefficients from water-extractable soil P were not significantly different for 17 of 20 soils, with values ranging from 6.0 to 18.3. The relationship between soil P sorption saturation and runoff FRP (microg L(-1)) was the same for all 10 soils investigated, exhibiting a split-line relationship where runoff FRP rapidly increased at P sorption saturation values greater than 12.5%. Overall, a single extraction coefficient (2.0 for Mehlich-3 P data, 11.2 for water-extractable P data, and a split-line relationship for P sorption saturation data) could be used in water quality models to approximate dissolved P release from soil to runoff for the majority of soil, hydrologic, or management conditions. A test for soil P sorption saturation may provide the most universal approximation, but only for noncalcareous soils.     

Trihalomethane reactivity of water- and sodium hydroxide-extractable organic carbon fractions from peat soils

Certain organic carbon moieties in drinking source waters of the Sacramento-San Joaquin Delta can react with chlorine during disinfection to form potentially carcinogenic and mutagenic trihalomethanes. The properties of reactive organic carbon in Delta waters, particularly those of soil origin, have been poorly understood. This study attempts to characterize trihalomethane reactivity of soil organic carbon from three representative Delta peat soils. Soil organic carbon was extracted from all three soils with either deionized H2O or 0.1 M NaOH and sequentially separated into humic acids, fulvic acids, and nonhumic substances for quantitation of trihalomethane formation potential. Water-extractable organic carbon represented only 0.4 to 0.7% of total soil organic carbon, whereas NaOH extracted 38 to 51% of total soil organic carbon. The sizes and specific trihalomethane formation potential (STHMFP) of individual organic carbon fractions differed with extractants. Fulvic acids were the largest fraction in H2O-extractable organic carbon, whereas humic acids were the largest fraction in NaOH-extractable organic carbon. Among the fractions derived from H2O-extractable carbon, fulvic acids had the greatest specific ultraviolet absorbance and STHMFP and had the majority of reactive organic carbon. Among the fractions from NaOH-extractable organic carbon, humic acids and fulvic acids had similar STHMFP and, thus, were equally reactive. Humic acids were associated with the majority of trihalomethane reactivity of NaOH-extractable organic carbon. The nonhumic substances were less reactive than either humic acids or fulvic acids regardless of extractants. Specific ultraviolet absorbance was not a good predictor of trihalomethane reactivity of organic carbon fractions separated from the soils.