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.     

Phosphorus sorption by sediments in a southeastern coastal plain in-stream wetland

A close relationship has been reported between sediment organic C (SedOC) content and its P sorption capacity (P(max)) and total P (TP) concentration. Phosphorus sorbed to organically complexed cations is a proposed explanation for this relationship. The objectives of this study were (i) to determine relationships between in-stream wetland SedOC content and both the sediment's P(max) and TP concentrations, and (ii) to ascertain the role of both organically complexed and oxalate-extractable cations on the sediment P(max) and TP values. The sediment's oxalate-extractable Fe (Fe(ox)) and Al (Al(ox)) contents were determined using acidified ammonium oxalate, while sodium pyrophosphate was used to extract organically complexed cations (Al(pryo), Ca(pyro), Fe(pyro), Mg(pyro), and Mn(pyro)). Both the sediment's P(max) and TP contents were strongly correlated with its SedOC concentration (r(2) > 0.90, P < 0.001). Only the Al(ox) contents were significantly correlated with TP and P(max), suggesting that amorphous Al forms have an important role in P sorption. All five pyrophosphate-extracted cations were significantly correlated with SedOC contents. Regression analyses showed that the Al(pyro) accounted for 88% of the variation in sediment P(max) values, whereas a combination of Al(pyro) and Ca(pyro) accounted for 98% of the variation in sediment TP concentrations. Additionally, Al and Ca chelated by SedOC compounds also have an important role in P binding and indicate that a linkage exists between the wetlands SedOC and P(max) content and its ability to accumulate TP. This study identified that two different mechanisms have significant roles in regulating P sorption by sediments in a southeastern Coastal Plain in-stream wetland.     

Uptake and release of phosphorus from overland flow in a stream environment

Phosphorus runoff from agricultural fields has been linked to fresh-water eutrophication. However, edge-of-field P losses can be modified by benthic sediments during stream flow by physiochemical processes associated with Al, Fe, and Ca, and by biological assimilation. We investigated fluvial P when exposed to stream-bed sediments (top 3 cm) collected from seven sites representing forested and agricultural areas (pasture and cultivated), in a mixed-land-use watershed. Sediment was placed in a 10-m-long, 0.2-m-wide fluvarium to a 3-cm depth and water was recirculated over the sediment at 2 L s(-1) and 5% slope. When overland flow (4 mg dissolved reactive phosphorus [DRP] and 9 mg total phosphorus [TP] L(-1)) from manured soils was first recirculated, P uptake was associated with Al and Fe hydrous oxides for sediments from forested areas (pH 5.2-5.4) and by Ca for sediments from agricultural areas (pH 6.5-7.2). A large increase (up to 200%) in readily available P NH4Cl fraction was noted. After 24 h, DRP concentration in channel flow was related to sediment solution P concentration at which no net sorption or desorption of P occurs (EPC0) (r2 = 0.77), indicating quasi-equilibrium. When fresh water (approximately 0.005 mg P L(-1) mean base flow DRP at seven sites) was recirculated over the sediments for 24 h, P release kinetics followed an exponential function. Microbial biomass P accounted for 34 to 43% of sediment P uptake from manure-rich overland flow. Although abiotic sediment processes played a dominant role in determining P uptake, biotic process are clearly important and both should be considered along with the location and management of landscape inputs for remedial strategies to be effective.     

Conditions affecting the release of phosphorus from surface lake sediments

Laboratory studies were conducted to determine the effect of pH and redox conditions, as well as the effect of Fe, Mn, Ca, Al, and organic matter, on the release of ortho-phosphates in lake sediments taken from Lakes Koronia and Volvi (Northern Greece). Results were evaluated in combination with experiments to determine P fractionation in the sediment. The study revealed the major effect of redox potential and pH on the release of P from lake sediments. Both lakes showed increased release rates under reductive conditions and high pH values. The fractionation experiments revealed increased mobility of the reductive P fraction as well as of the NaOH-P fraction, indicating participation of both fractions in the overall release of sediment-bound P, depending on the prevailing environmental conditions. The results were assessed in combination with the release patterns of Fe, Mn, Ca, Al, and organic matter, enabling the identification of more specific processes of P release for each lake. The basic release patterns included the redox induced reductive dissolution of P-bearing metal oxides and the competitive exchange of phosphate anions with OH- at high pH values. The formation of an oxidized surface microlayer under oxic conditions acted as a protective film, preventing further P release from the sediments of Lake Volvi, while sediments from Lake Koronia exhibited a continuous and increased tendency to release P under various physicochemical conditions, acting as a constant source of internal P loading.     

Soil and litter phosphorus-31 nuclear magnetic resonance spectroscopy: extractants, metals, and phosphorus relaxation times

Phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy is an excellent tool with which to study soil organic P, allowing quantitative, comparative analysis of P forms. However, for 31P NMR to be tative, all peaks must be completely visible, and in their correct relative proportions. There must be no line broadening, and adequate delay times must be used to avoid saturation of peaks. The objective of this study was to examine the effects of extractants on delay times and peak saturation. Two samples (a forest litter and a mineral soil sample) and three extractants (0.25 M NaOH, NaOH plus Chelex (Bio-Rad Laboratories, Hercules, CA), and NaOH plus EDTA) were used to determine the differences in the concentration of P and cations solubilized by each extractant, and to measure spin-lattice (T1) relaxation times of P peaks in each extract. For both soil and litter, NaOH-Chelex extracted the lowest concentrations of P. For the litter sample, T1 values were short for all extractants due to the high Fe concentration remaining after extraction. For the soil sample, there were noticeable differences among the extractants. The NaOH-Chelex sample had less Fe and Mn remaining in solution after extraction than the other extractants, and the longest delay times used in the study, 6.4 s, were not long enough for quantitative analysis. Delay times of 1.5 to 2 s for the NaOH and NaOH-EDTA were adequate. Line broadening was highest in the NaOH extracts, which had the highest concentration of Fe. On the basis of these results, recommendations for future analyses of soil and litter samples by solution 31P NMR spectroscopy include: careful selection of an extractant; measurement of paramagnetic ions extracted with P; use of appropriate delay times and the minimum number of scans; and measurement of T1 values whenever possible.     

A comparison of phosphorus speciation and potential bioavailability in feed and feces of different dairy herds using 31p nuclear magnetic resonance spectroscopy

An experiment was conducted to examine how potential phosphorus (P) bioavailability (inferred from speciation) differs in feed and feces collected in spring from four dairy herds representing different management systems: (i) total confinement with cows fed total mixed ration (TMR), (ii) total confinement with TMR plus P mineral supplement, (iii) a hybrid of confinement with TMR and pastoral grazing, and (iv) predominantly grazing with supplemental grains. A treatment was included that air dried feces to simulate conditions after dung deposition. Wet chemical techniques and solution (31)P nuclear magnetic resonance spectroscopy ((31)P-NMR) were used to identify P concentrations and compounds present in water (a surrogate for P in overland flow), dilute acid (0.012 M HCl, an estimate of P utilization by cattle), or NaOH-EDTA (a solution that maximizes the organic P extraction) extracts of feed and feces. In general, P concentration in feces paralleled P in feed. Air drying feces decreased water-extractable P by 13 to 61% largely due to a decrease in orthophosphate, whereas NaOH-EDTA-extractable P increased by 18 to 48%. Analysis of dilute HCl was unsuccessful due to orthophosphate precipitation when pH was adjusted to 12 for (31)P-NMR. In water extracts, more P was in bioavailable diester-P forms, undetectable by colorimetry, than in NaOH-EDTA extracts. In feed, orthophosphate dominated (46-70%), but myo-IHP varied with feed (<10% in forage samples but 43% in a TMR sample). The proportion of myo-IHP decreased in feces compared with feed via mineralization but decreased less in systems with a greater proportion of available P input (e.g., orthophosphate and phospholipids). Feed and drying effect the concentrations and forms of P in feces and their potential impact on soil and water quality. Although bioavailable P in feces from pasture-based and confined systems can be similar in spring, dung-P is distributed on a lower kg P ha(-1) rate in grazing systems. The best method to mitigate P loss from feces is to decrease P in feed.     

Phosphorus mobilization from various sediment pools in response to increased pH and silicate concentration

Phosphorus (P) release from sediment particles to the interstitial water has been studied extensively, but the contribution of different inorganic P pools in sediment under differing environmental conditions is not fully understood. This study was undertaken to get more detailed information about the chemical mobilization mechanisms. Phosphorus mobilization from reserves bound by Al, Fe, and Ca compounds in response to increased pH and to inorganic silicon (Si) enrichments was investigated using a sequential fractionation analysis and an isotope-labeling technique. The aerobic sediment of Lake Vesij?rvi had a high P retention capacity, and Fe-bound P was the largest inorganic P pool as well as the main source of released P. High Si addition (47 mg Si L-1 sediment) released more P to the interstitial water than did the elevation of pH from 6.6 to 9.5, since Si lowered the resorption of released P onto hydrated Al oxides. This finding reveals that P equilibrium between Fe-bound and Al-bound P in sediments regulates P net mobilization to the interstitial water under aerobic conditions. Furthermore, elevated pH combined with high Si enrichment had a positive synergistic effect, resulting in the most substantial P mobilization. This synergism may cause a self-fueled increase in the internal loading of P. It accentuates the effect of diatom sedimentation on P fluxes in eutrophic lakes with high pH and may favor the appearance of bloom-forming cyanobacteria.     

Agri-environmental thresholds using Mehlich III soil phosphorus saturation index for vegetables in histosols

The P concentration in Norton Creek which drains cultivated Histosols in Quebec showed median concentration exceeding up to 14 times the environmental guideline of 0.03 mg total P L(-1). The aim of this study was to develop environmental and agronomic thresholds using soil tests to provide a tool for P management in Histosols. Soil samples were collected from Histosols across Quebec (82) and in fertilizer trials (66) to calibrate soil test methods against the degree of P saturation (DPS(OX)) using the acid-oxalate method and setting alpha(m) = 0.4, and the water-extractable P (P(W)) (Sissingh, 1971). The field trials on crop response to added P were conducted with carrots (8), potatoes (11), onions (10), Chinese cabbage (7), celery (10), and lettuce (20). Relative yields were computed as yield in control without P divided by highest yield with added P. The Mehlich III (M-III) P extraction was more closely related (r(2) = 0.73) to DPS(OX) than the Bray 1 method (r(2) = 0.62) and the Florida extraction method (r(2) = 0.53). The [P/(Al+gammaFe)](M-III) ratio as index of P saturation (IPS(M-III)) was the most closely related to DPS(OX) (r(2) = 0.88) setting gamma = 5. The critical [P/(Al+5Fe)](M-III) ratio of 0.05 at DPS(OX) = 0.25 and P(W) = 9.7 mg P L(-1) was validated by an independent study from North Carolina. The soil group (low- vs. high-IPS(M-III) soils) significantly influenced crop response to added P. Critical agronomic IPS(M-III) values were found between 0.10 and 0.15. Those environmental and agronomic benchmarks are instrumental for managing the P in vegetable-grown Histosols.     

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.     

Characteristics of slag, fly ash and deposited particles during melting of dewatered sewage sludge in a pilot plant

This study examines slag, fly ash, and deposited particles during melting of dewatered sewage sludge in a pilot plant. In addition, the chemical composition of particles in flue gas was simulated using a thermodynamics program, namely FACTSage 5.2. The results showed that the main components of slag were Al, Fe, Ca, P and Si; the minor components were Na, K, Mg, Cu, and Zn. The main chemical compound of slag was Ca4(Mg,Fe)5(PO4)6. For fly ash particles, heavy metals with the highest concentrations were in the order of Zn and As, Pb, Cu, and Cd, respectively. For non-heavy metals, Al, Fe and P were also found in significant amounts. The majority of deposited particles were composed of elements of Zn, P, S, Na, Fe, Al, Si, and Ca and such chemical compounds as Zn3(PO4)2, AlPO4, FePO4 and Fe(OH)3 while the minority consisted of elements of As, Cu, and Pb. Moreover, the compositions of deposited particles in each chamber differed due to different flue gas temperatures inside. In the secondary chamber at 760 degrees C, the amounts of Fe and Al were higher than Zn, whereas, in the other chambers (600-400 degrees C), the amount of Zn was higher. In other words, at the lower temperature the deposition of Zn was higher than the deposition of Fe and Al. In the water cooling section, volatile elements (i.e. Zn, As, Cu, Pb) were found in the highest concentrations due to a big difference in temperature between the wall surface and flue gas. From the simulation results, most of the elements in the gas phase were found to be chloride compounds, whereas those in the solid phase were in the form of oxide, sulfate, and phosphate compounds.     

Phosphorus adsorption and desorption potential of stream sediments and field soils in agricultural watersheds

Phosphorus release from stream sediments into water could increase P loads leaving agricultural watersheds and contribute to lag-time between implementation of best management practices and improvement in water quality. Improved understanding of P release from stream sediments can assist in setting water quality goals and designing stream monitoring programs. The objective of this study was to estimate the relative potential of sediments and soils to release P to stream water in two agricultural watersheds. Stream sediments were collected from banks, pools, riffles, and depositional features. Soils were sampled from wheat, row crop, pasture, and manure-amended fields. Sediments and soils were analyzed for equilibrium P concentration at zero net P sorption (EPC0), maximum P adsorption capacity (P(max)), anion exchange extractable P (P(lab)), and degree of P saturation. Dissolved reactive P (DRP) of stream water was monitored. Stream sediment EPC0 was similar to or less than EPC0 from field soils; however, P(lab) of stream sediments was three times less than field soils. Sediments were sandy and had low P(max) due to low oxalate-extractable Fe and Al, which could be explained by stream geomorphology. Manure-amended fields had the highest EPC0 and P(lab) due to continued inputs of manure-based P; however, conventionally fertilized fields also represented an important P source due to their vast extent. Stream water DRP was similar to EPC0 of sediments during base flow and similar to EPC0 of field soils during storm flow. These results indicate that sediments in these streams are a relatively minor P source.     

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

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

In situ removal of copper from sediments by a galvanic cell

This study dealt with in situ removal of copper from sediments through an electrokinetic (EK) process driven by a galvanic cell. Iron (Fe) and carbon (C) were placed separately and connected with a conductive wire. Polluted sediments were put between them and water was filled above the sediments. The galvanic cell was thus formed due to the different electrode potentials of Fe and C. The cell could remove the pollutants in the sediments by electromigration and/or electroosmosis. Results showed that a weak voltage less than 1V was formed by the galvanic cell. The voltage decreased with the increase of time. A slight increase of sediment pH from the anode (Fe) to the cathode (C) was observed. The presence of supernatant water inhibited the variation of sediment pH because H(+) and OH(-) could diffuse into the water. The removal of copper was affected by the sediment pH and the distribution of electrolyte in sediment and supernatant water. Lower pH led to higher removal efficiency. More electrolyte in the sediment and/or less electrolyte in the supernatant water favored the removal of copper. The major removal mechanism was proposed on the basis of the desorption of copper from sediment to pore solution and the subsequent electromigration of copper from the anode to the cathode. The diffusion of copper from sediment to supernatant water was negligible.     

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.     

Fate and toxicity of endosulfan in Namoi River water and bottom sediment

Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P < 0.05) more concentrated on the large (>63 microm) particle fraction compared with smaller size fractions (<5 microm and 5-24 microm) of bottom sediments from the Namoi River, Australia. Following completion of the particle size fractionation (6 to 12 wk) and a sediment toxicity assessment (2 wk), the sediments showed large decreases in concentrations of alpha-endosulfan that coincided with an increase in endosulfan sulfate concentrations and minimal changes in beta-endosulfan concentrations. In the Namoi River, similar patterns were observed in the composition of total endosulfan in monthly measurements of bottom sediments and in passive samplers placed in the water column following runoff from cotton (Gossypium hirsutum L.) fields. The toxicity of endosulfan sulfate in river water indicated by the nymphs of the epibenthic mayfly Jappa kutera, was more persistent than the alpha- and beta-endosulfan parent isomers due to its longer half-life. This suggests that endosulfan sulfate would contribute most to previously observed changes in population densities of aquatic biota. Measured concentrations of total endosulfan in river water of up to 4 microg L(-1) following storm runoff, exceed the range of the 96-h median lethal concentration (LC50) values in river water for both alpha-endosulfan (LC50 = 0.7 microg L(-1); 95% confidence interval [CI] = 0.5 to 1.1) and endosulfan sulfate (LC50 = 1.2 microg L(-1); 95% CI = 0.4 to 3.3). In contrast, the 10-d LC50 value for total endosulfan in the sediment toxicity test (LC50 = 162 microg kg(-1); 95% CI = 120 to 218 microg kg(-1)) was more than threefold higher than the highest measured concentration of total endosulfan in field samples of bottom sediment (48 microg kg(-1)). This suggests that pulse exposures of endosulfan in the water column following storm runoff may be more acutely toxic to riverine biota than in contaminated bottom sediment.     

Phosphorus and other soil components in a dairy effluent sprayfield within the central Florida Ridge

There is concern that P from dairy effluent sprayfields will leach into groundwater beneath Suwannee River basins in northern Florida. Our purpose was to describe the effects of dairy effluent irrigation on the movement of soil P and other nutrients within the upper soil profile of a sprayfield over three 12-mo cycles (April 1998-March 2001). Effluent P rates of 70, 110, and 165 kg ha(-1) cycle(-1) were applied to forages that were grown year-round. The soil is a deep, excessively drained sand (thermic, uncoated Typic Quartzipsamment). Mean P concentration in soil water below the rooting zone (152-cm depth) was < or = 0.1 mg L(-1) during 11 3-mo periods. Mehlich-1-extractable (M1) P, Al, and Ca in the topsoil increased over time but did not change in subsoil depths of 25 to 51, 51 to 71, 71 to 97, and 97 to 122 cm. Topsoil Ca increased as effluent rate increased. High Ca levels were found in dairy effluent (avg.: 305 mg L(-1)) and supplemental irrigation water (avg.: 145 mg L(-1)) which likely played a role in retaining P in the topsoil. An effect of effluent rate on P and Al concentrations in the topsoil was not detected, probably due to large and variable quantities present at project initiation. The P retention capacity (i.e., Al plus Fe) increased in the topsoil because Al increased. Dairy effluent contained Al (avg.: 31 mg L(-1)). Phosphorus saturation ratio (PSR) increased over time in the topsoil but not in subsoil layers. Regardless of effluent rate, the P retention capacity and PSR of subsoil, which contained 119 to 229 mg kg(-1) of Al, should be taken into account when assessing the risk of P moving below the rooting zone of most forage crops.     

Organic ligand effects on enzymatic dephosphorylation of myo-inositol hexakis dihydrogenphosphate in dairy wastewater

Animal manure contains partially digested feed fiber and grains where phosphorus (P) is bound in organic compounds that include myo-inositol 1,2,3,5/4,6-hexakis dihydrogenphosphate or phytic acid (IP6). Information is needed on the effects of other (non-IP6) organic ligands (LIGND) on the enzymatic dephosphorylation of IP6, which is a potential source of dissolved orthophosphate P (PO4-P) in the soil-manure-water system. The effects of 1,2-cyclohexane diamino-tetraacetate (CDTA), diethylenetriamine-N,N,N',N',N'-pentaacetate (DTPA), ethylenediamine-N,N,N',N'-tetraacetate (EDTA), oxalate (OXA), and phthalate (PHTH) and LIGND to IP6 molar ratio and charge concentration ratio on IP6 dephosphorylation were studied to determine controlling mechanisms of IP6 persistence in manure. Solution PO4-P concentrations were analyzed by ion chromatography as the phosphomolybdate-ascorbic acid method partly includes IP6-P. Uncomplexed IP6 dephosphorylation by Aspergillus ficuum (Reichardt) Henn. phytase EC 3.1.3.8 at pH 4.5 and 6 is unaffected by the presence of LIGNDs. As the concentrations of Ca2+, Al3+, or Fe3+ increase, dephosphorylation is reduced. Their inhibitory effect lessens in the presence of LIGNDs, in the following order: CDTA = EDTA > DTPA > OXA > or = PHTH. Whether CDTA or EDTA is the most effective LIGND depends upon the acidity of the suspension and LIGND charge concentration, reducing the inhibitory effect of polyvalent counterions to the point of promoting the hydrolysis of a manure phytase-hydrolyzable phosphorus (PHP) fraction that is otherwise unavailable. Therefore, ligand-induced changes increase the mobilization and dephosphorylation of complexed organic P, above and beyond the simple dissolution of inorganic phosphates. An analytical method for potentially bioavailable PHP in animal manure should include a LIGND as extracting reagent. Also, potential LIGNDs in an organic carbon-rich dairy wastewater may increase the release of PHP and environmental dispersion of PO4-P.     

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.     

Effect of cobalt sorption on metal fractionation in anaerobic granular sludge

A sequential extraction procedure was applied to two anaerobic methanogenic sludges (Eerbeek and Nedalco) to examine the speciation of micro- and macronutrients in the sludges after cobalt sorption by exposing the sludge to a 1 mM Co solution for 4 d at pH 7 and 30 degrees C. The effect of different physicochemical conditions on cobalt sorption was studied as well: effect of pH (6-8), effect of competition by a second trace element (Ni or Fe), modification of the granular matrix by glutaraldehyde or heat treatment, and EDTA (ethylenediaminetetraacetic acid) addition. Sorbed Co was found to distribute between the carbonates, organic matter + sulfides, and residual fractions. Cobalt adsorption resulted in an antagonistic interaction with other metals present in the granular matrix, evidenced by the solubilization of other trace elements (e.g., Ni, Cu, and Zn) as well as macronutrients (especially Ca and Fe). Modification of the sludge matrix by glutaraldehyde or heat treatment, or exposure to EDTA, led to serious modifications of the Co sorption capacity and strong interactions with multivalent cations (i.e., Ca(2+) and Fe(2+)).     

The release of phosphorus to porewater and surface water from river riparian sediments

Sediments can be both a source and a sink of dissolved phosphorus (P) in surface water and shallow groundwater. Using laboratory mesocosms, we studied the influence of flooding with deionized water and simulated river water on P release to solution using sediment columns taken from a riparian wetland. The mesocosm incubation results showed that rather than retaining nutrients, sediments in the riparian zone may be a significant source of P. Concentrations of dissolved P in porewater reached more than 3 mg L(-1) and in surface water over 0.8 mg L(-1) within a month of sediment inundation. The reductive dissolution of P-bearing iron (Fe) oxides was the likely mechanism responsible for P release. Dissolved P to Fe molar ratios in anaerobic samples were approximately 0.45 when columns were flooded with water that simulated the chemistry of the adjacent river. This suggests there was insufficient Fe in the anaerobic samples to precipitate all P if the solutions were oxygenated or transported to an aerobic environment. If the anaerobic wetland solutions were delivered to oxygenated rivers and streams adjacent to the riparian zone, the equilibrium concentration of P in these systems could rise. The timing of P release was inversely related to the nitrate (NO3-) concentration in floodwater. This indicates that in riparian zones receiving low nitrate loads, or where NO3- loads are being progressively reduced, the risk of dissolved P release may increase. These findings present particular challenges for restoration and management in riparian areas.