Internal phosphorus loading in a chain of eutrophic hardwater lakes in Saskatchewan, Canada.

Sediments can act as a source or sink of phosphorus (P) for the water column of lakes. In iron (Fe)-rich softwater lakes, redox processes are important contributors to sediment P flux. However, the contribution of redox processes to P flux in hardwater lakes, with high pH and high concentrations of redox-insensitive calcium (Ca) is unknown. Intact sediment cores, collected in different seasons (summer or fall) from a chain of eutrophic hardwater lakes in southeastern Saskatchewan, Canada, were used to quantify sediment P fluxes in laboratory incubations under hypoxic or oxic conditions at temperatures consistent with the season of sample collection. Geochemical analyses determined concentrations of sediment total (TP) and organic P (TPo), organic matter (OM), total Ca and magnesium, and total and extractable manganese, Fe and aluminum. Sediment P pools were determined using sequential fractionation and solution 31P nuclear magnetic resonance spectroscopy. Sediment P fluxes were significantly higher in sediment cores incubated under hypoxic conditions (-24.4 to 28.5 mg P m-2 d-1) than oxic conditions (-60.3 to 14.2 mg P m-2 d-1). There were significant seasonal and lake differences for TP, TPo and cation concentrations, with Ca the dominant cation in all but one lake. Phosphate bound in the redox-sensitive pool was the only sediment P fraction that significantly differed among the lakes (0.10 to 0.18 mg P g-1 d.w.; 9 to 16 % of TP), with an inverse relationship to sediment P flux. Principal component analysis suggests that high concentrations of internally-generated TPo forms and OM in surface sediments play a key role in internal P loading in these lakes. However, sediment Ca appears to have an overriding effect on sediment P, partially masking the impact of redox control on internal P loading in these hardwater prairie lakes.

Maize-soybean intercropping facilitates chemical and microbial transformations of phosphorus fractions in a calcareous soil.

Intercropping often substantially increases phosphorus (P) availability to plants compared with monocropping, which could be an effective strategy for soil legacy P recovery and agricultural production. However, the biogeochemical interactions among plants, microbes, and soil that mobilize P remain largely unknown in intercropping systems. Pot experiments with maize-soybean intercropping in a calcareous soil were conducted to investigate the potential chemical and biological transformation mechanisms of inorganic P (Pi) and organic P (Po) using sequential extraction and Illumina MiSeq sequencing. Compared to monocropping of each crop, maize-soybean intercropping significantly enhanced total P uptake of the two crops by mobilizing Ca2-Pi [extracted by bicarbonate (NaHCO3)], Al-Pi/Po [extracted by ammonium fluoride (NH4F)] and Fe-Pi [extracted by sodium hydroxide and sodium carbonate (NaOH-Na2CO3)] fractions. Furthermore, there were significant increases in the organic carbon content and alkaline phosphomonoesterase (ALP) and phosphodiesterase (PDE) activities as well as the abundances of Microvirga, Lysobacter, Microlunatus and Sphingomonas under maize-soybean intercropping relative to monocropping. In contrast, compared to monocroppping, no significant change in the soil pH was observed under maize-soybean intercropping. Therefore, the enhanced P uptake of the maize-soybean intercropping probably resulted from a synergistic effect of rhizosphere organic carbon deposit, increased activities of ALP and PDE, together with the bacteria (Microvirga, Lysobacter, Microlunatus and Sphingomonas) which showed correlation with soil P forms, while the generally recognized rhizosphere acidification was excluded in this investigated calcareous soil. Moreover, the selected bacterial genera exhibited a closer network in the rhizosphere of soybean compared to maize, suggesting enhanced interactions among bacteria in the soybean rhizosphere. These results provide theoretical bases for the recovery of soil legacy P by maize-soybean intercropping.

Soil Depth Significantly Shifted Microbial Community Structures and Functions in a Semiarid Prairie Agroecosystem.

The North American Great Plains cover a large area of the Nearctic ecozone, and an important part of this biome is semiarid. The sustainable intensification of agriculture that is necessary to produce food for an ever-increasing world population requires knowledge of the taxonomic and functional structure of the soil microbial community. In this study, we investigated the influence of soil depth on the composition and functions of the microbial communities hosted in agricultural soils of a semiarid agroecosystem, using metagenomic profiling, and compared them to changes in soil chemical and physical properties. Shotgun sequencing was used to determine the composition and functions of the soil microbial community of 45 soil samples from three soil depths (0-15 cm, 15-30 cm, and 30-60 cm) under different agricultural land use types (native prairie, seeded prairie, and cropland) in southwest Saskatchewan. Analysis of community composition revealed the declining abundance of phyla Verrucomicrobia, Bacteroidetes, Chlorophyta, Bacillariophyta, and Acidobacteria with soil depth, whereas the abundance of phyla Ascomycota, Nitrospirae, Planctomycetes, and Cyanobacteria increased with soil depth. Soil functional genes related to nucleosides and nucleotides, phosphorus (P) metabolism, cell division and cell cycle, amino acids and derivatives, membrane transport, and fatty acids were particularly abundant at 30-60 cm. In contrast, functional genes related to DNA and RNA metabolism, metabolism of nitrogen, sulfur and carbohydrates, and stress response were more abundant in the top soil depth. The RDA analysis of functional genes and soil physico-chemical properties revealed a positive correlation between phages and soil organic P concentrations. In the rooting zone of this semiarid agroecosystem, soil microbes express variable structural patterns of taxonomic and functional diversity at different soil depths. This study shows that the soil microbial community is structured by soil depth and physicochemical properties, with the middle soil depth being an intermediate transition zone with a higher taxonomic diversity. Our results suggest the co-existence of various microbial phyla adapted to upper and lower soil depths in an intermediate-depth transition zone.

Land use and landscape position influence soil organic phosphorus speciation in a mixed land use watershed.

Land use can significantly alter soil P forms, which will influence P loss in runoff. Organic P (Po ) compounds are an important component of soil P, but their forms and cycling in soils with different land uses are still poorly understood. In addition, streambanks are potential sources of P loss; P forms and concentrations in streambank soils may vary with land use, affecting potential P loss to water. This study used solution 31 P nuclear magnetic resonance spectroscopy to characterize and quantify P in interior and streambank soils (0-10 cm) under duplicate sites from four different land uses along streams in the Missisquoi River basin (VT, USA): silage corn, hay meadow, emergent wetlands, and forest. Orthophosphate monoesters were the dominant P compound class regardless of land use or landscape position. Forest soils had the lowest Po concentrations, less labile P forms than other soils, and significantly lower concentrations of total inositol hexakisphosphates and total orthophosphate monoesters compared with corn soils. Riparian buffer zones for agricultural soils lowered P concentrations in streambank soils for many soil P pools relative to interior soils. The wetland soils of this study had P concentrations and P forms that were similar to those for interior agricultural soils and generally showed no reduction in P concentrations in streambank soils relative to interior soils. This is consistent with the role of wetlands as P sinks in the landscape but also suggests these wetlands should be carefully monitored to minimize P accumulation, especially in streambank soils.

Potential Phosphorus Export in Snowmelt as Influenced by Fertilizer Placement Method in the Canadian Prairies.

Placement strategies for P fertilizer can affect P availability to crops and influence the amounts and forms of P removed from soil in runoff, contributing to eutrophication. On the Canadian prairies, most runoff occurs during snowmelt. Two adjacent farm fields in Saskatchewan, Canada, were used to assess the effects of spring P fertilizer placement on crop P uptake, residual soil P, and potential P export in simulated snowmelt. One was in conventional tillage (CT) with no history of P fertilization, and the other was in a no-till (NT) system with multiyear P fertilization at recommended rates. Fertilization (monoammonium phosphate) treatments were no P fertilizer (control); seed placed, deep banded, and broadcast and incorporated at 20 kg PO ha; and broadcast treatments at 20, 40, and 80 kg PO ha. Yield and P uptake were not affected by placement method. Water-extractable P at the soil surface after harvest was unaffected by placement or rate at either site but increased below the 5-cm depth at the NT site in 2016. Broadcast treatments increased P in runoff relative to in-soil P placement for the 20- and 80-kg PO ha treatments at the CT site and for the 80-kg PO ha treatment at the NT site. Thus, in-soil application of P fertilizer appears to be an effective strategy to reduce the risk of P export in snowmelt runoff.

Long-Term Land Use Affects Phosphorus Speciation and the Composition of Phosphorus Cycling Genes in Agricultural Soils.

Agriculturally-driven land transformation is increasing globally. Improving phosphorus (P) use efficiency to sustain optimum productivity in diverse ecosystems, based on knowledge of soil P dynamics, is also globally important in light of potential shortages of rock phosphate to manufacture P fertilizer. We investigated P chemical speciation and P cycling with solution 31P nuclear magnetic resonance, P K-edge X-ray absorption near-edge structure spectroscopy, phosphatase activity assays, and shotgun metagenomics in soil samples from long-term agricultural fields containing four different land-use types (native and tame grasslands, annual croplands, and roadside ditches). Across these land use types, native and tame grasslands showed high accumulation of organic P, principally orthophosphate monoesters, and high acid phosphomonoesterase activity but the lowest abundance of P cycling genes. The proportion of inositol hexaphosphates (IHP), especially the neo-IHP stereoisomer that likely originates from microbes rather than plants, was significantly increased in native grasslands than croplands. Annual croplands had the largest variances of soil P composition, and the highest potential capacity for P cycling processes based on the abundance of genes coding for P cycling processes. In contrast, roadside soils had the highest soil Olsen-P concentrations, lowest organic P, and highest tricalcium phosphate concentrations, which were likely facilitated by the neutral pH and high exchangeable Ca of these soils. Redundancy analysis demonstrated that IHP by NMR, potential phosphatase activity, Olsen-P, and pH were important P chemistry predictors of the P cycling bacterial community and functional gene composition. Combining chemical and metagenomics results provides important insights into soil P processes and dynamics in different land-use ecosystems.

Phosphorus Leaching from Soil Cores from a Twenty-Year Study Evaluating Alum Treatment of Poultry Litter.

Adding alum to poultry litter is a best management practice used to stabilize P in less soluble forms, reducing nonpoint-source P runoff. However, little research has been conducted on how alum additions to litter affect subsequent leaching of P from soil. The objective of this study was to evaluate the effects of alum-treated versus untreated poultry litter on P leaching from soil cores receiving long-term poultry litter applications. Two intact soil cores were taken from each of 52 plots in a long-term study with 13 treatments: a control, four rates each of untreated and alum-treated litter (2.24, 4.49, 6.72, and 8.96 Mg ha), and four rates of ammonium nitrate (65, 130, 195, and 260 kg N ha). One core from each plot received the same fertilizer as for the previous 20 yr, whereas the other was unfertilized in the study year, resulting in a total of 25 treatments. Cores were exposed to natural rainfall, and P leaching was measured for 1 yr. The average soluble reactive P concentrations in the leachate varied from 0.16 to 0.44 mg P L in fertilized alum-treated cores, whereas leachate from cores fertilized with untreated litter ranged from 0.40 to 2.64 mg P L. At the highest litter rate (8.96 Mg ha), alum reduced total dissolved P and total P concentrations in leachate by 83 and 80%, respectively, compared with untreated litter. These results indicate that alum additions to poultry litter significantly reduced soluble and total P fractions in leachate.

The Contrasting Effects of Alum-Treated Chicken Manures and KH2PO4 on Phosphorus Behavior in Soils.

Alum [KAl(SO)⋅12HO] is often added to chicken manure to limit P solubility after land application. This is generally ascribed to the formation of Al-PO complexes. However, Al-PO complex formation could be affected by the matrix of chicken manure, which varies with animal diet. Alum was added to KHPO (as a reference material) and two manures from typical chicken farms in China, one from an intensive farm (CMIF) and another from free-ranging chickens (CMFR). These were subsequently incubated with soils for 100 d to investigate P transformations. Alum reduced water-soluble colorimetrically reactive phosphorus (RP) from soils amended with manure more effectively than in soils amended with KHPO. Alum addition lowered Mehlich-3 RP in soils with CMFR but had no influence on Mehlich-3 RP in CMIF- or KHPO-amended soils. A comparison of P in digested Mehlich-3 extracts with RP in undigested samples showed significantly increased P in digests of alum-treated CMFR only. Fractionation data indicated that alum treatment increased P in the NHF-RP (Al-P) fraction only in soils with KHPO, but not in soils with manure treatments. Furthermore, NaOH-extracted nonreactive P was markedly higher in soil with alum-treated CMFR relative to normal CMFR. The CMFR manure was assumed to contain higher concentrations of organic P because these chickens were fed grains only. These results suggest that the formation of alum-organic P complexes may reduce P solubility. By comparing alum-treated KHPO and manures, it appears that organic matter in manure could interfere with the formation of Al-PO complexes.

Phosphorus acquisition by citrate- and phytase-exuding Nicotiana tabacum plant mixtures depends on soil phosphorus availability and root intermingling.

Citrate and phytase root exudates contribute to improved phosphorus (P) acquisition efficiency in Nicotiana tabacum (tobacco) when both exudates are produced in a P deficient soil. To test the importance of root intermingling in the interaction of citrate and phytase exudates, Nicotiana tabacum plant-lines with constitutive expression of heterologous citrate (Cit) or fungal phytase (Phy) exudation traits were grown under two root treatments (roots separated or intermingled) and in two soils with contrasting soil P availability. Complementarity of plant mixtures varying in citrate efflux rate and mobility of the expressed phytase in soil was determined based on plant biomass and P accumulation. Soil P composition was evaluated using solution 31 P NMR spectroscopy. In the soil with limited available P, positive complementarity occurred in Cit+Phy mixtures with roots intermingled. Root separation eliminated positive interactions in mixtures expressing the less mobile phytase (Aspergillus niger PhyA) whereas positive complementarity persisted in mixtures that expressed the more mobile phytase (Peniophora lycii PhyA). Soils from Cit+Phy mixtures contained less inorganic P and more organic P compared to monocultures. Exudate-specific strategies for the acquisition of soil P were most effective in P-limited soil and depended on citrate efflux rate and the relative mobility of the expressed phytase in soil. Plant growth and soil P utilization in plant systems with complementary exudation strategies are expected to be greatest where exudates persist in soil and are expressed synchronously in space and time.

Characterizing the phosphorus forms extracted from soil by the Mehlich III soil test.

Phosphorus (P) can limit crop production in many soils, and soil testing is used to guide fertilizer recommendations. The Mehlich III (M3) soil test is widely used in North America, followed by colorimetric analysis for P, or by inductively coupled plasma-based spectrometry (ICP) for P and cations. However, differences have been observed in M3 P concentrations measured by these methods. Using 31P nuclear magnetic resonance (P-NMR) and mass spectrometry (MS), we characterized P forms in M3 extracts. In addition to the orthophosphate that would be detected during colorimetric analysis, several organic P forms were present in M3 extracts that would be unreactive colorimetrically but measured by ICP (molybdate unreactive P, MUP). Extraction of these P forms by M3 was confirmed by P-NMR and MS in NaOH-ethylenediaminetetraacetic acid extracts of whole soils and residues after M3 extraction. The most abundant P form in M3 extracts was myo-inositol hexaphosphate (myo-IHP, phytate), a compound that may not contribute to plant-available P if tightly sorbed in soil. Concentrations of myo-IHP and other organic P forms varied among soils, and even among treatment plots on the same soil. Extraction of myo-IHP in M3 appeared to be linked to cations, with substantially more myo-IHP extracted from soils fertilized with alum-treated poultry litter than untreated litter. These results suggest that ICP analysis may substantially over-estimate plant-available P in samples with high MUP concentrations, but there is no way at present to determine MUP concentrations without analysis by both colorimetry and ICP. This study also tested procedures that will improve future soil P-NMR studies, such as treatment of acid extracts, and demonstrated that techniques such as P-NMR and MS are complimentary, each yielding additional information that analysis by a single technique may not provide.

Molecular speciation and transformation of soil legacy phosphorus with and without long-term phosphorus fertilization: Insights from bulk and microprobe spectroscopy.

Soil legacy phosphorus (P) represents a substantial secondary P resource to postpone the global P crisis. To fully utilize this P reserve, the transformation of legacy P speciation in a black soil with and without P fertilization for 27 years was investigated by chemical fractionation, molecular-level bulk (P K-edge X-ray absorption near-edge, XANES; solution 31P nuclear magnetic resonance) and microprobe (µ-X-ray fluorescence and µ-XANES) spectroscopy. Results from both fractionation and P bulk-XANES concordantly indicated that Ca2-P [Ca(H2PO4)2] acts as a reserve of labile P in response to soils with or without P fertilization. Cropping for 27 years depleted hydroxyapatite while enriched iron-bound P in soils irrespective of P application. Similar accumulation of soil organic P (Po), probably due to root residue inputs, occurred in both soils with and without P fertilization; the accumulated Po was present as orthophosphate diesters in soils with P fertilization more than in soils without P fertilization, suggesting that the release of labile Po was triggered by soil P deficits. These results provide vital information for agronomically and environmentally sustainable P management by demonstrating the potential crop availability of legacy soil P, which could reduce future P fertilization.

Soil organic phosphorus transformations during 2000 years of paddy-rice and non-paddy management in the Yangtze River Delta, China.

The contents and properties of soil organic phosphorus (Po) largely drive ecosystem productivity with increasing development of natural soil. We hypothesized that soil Po would initially increase with paddy management and then would persist under steady-state conditions. We analyzed soils from a 2000-year chronosequence of a rice-wheat rotation and an adjacent non-paddy 700-year chronosequence in Bay of Hangzhou (China) for their Po composition using solution 31P-NMR after NaOH-EDTA extraction. Land reclamation promoted Po accumulation in both paddy and non-paddy topsoils (depths ≤ 18 cm) until steady-state equilibria were reached within 200 years of land use. Greater Po concentrations were found, however, in the non-paddy subsoils than in those under paddy management. Apparently, the formation of a dense paddy plough pan hindered long-term Po accumulation in the paddy subsoil. The surface soils showed higher proportions of orthophosphate diesters under paddy than under non-paddy management, likely reflecting suppressed decomposition of crop residues despite elevated microbial P compounds stocks under anaerobic paddy-rice management. Intriguingly, the composition of Po was remarkably stable after 194-years of paddy management and 144-years of non-paddy management, suggesting novel steady-state equilibria of P dynamics had been reached in these man-made ecosystems after less than two centuries.

Long-term Changes in Grassland Soil Phosphorus with Fertilizer Application and Withdrawal.

Long-term phosphorus (P) applications can increase soil P concentrations in excess of agronomic optima, posing a risk to water quality. Once fertilization stops, however, it may take time for soil P concentrations to decline. Whereas P fertilization adds orthophosphate, little is known about changes in other soil P forms during P buildup and drawdown. This study examined changes in P pools (total P, Olsen P, Mehlich P, and water-extractable P) and P forms determined by P-nuclear magnetic resonance spectroscopy (P-NMR) in grazed grassland plots from Northern Ireland. Between 1994 and 1999, all plots received 8.3 kg P ha yr with variable rates of nitrogen (100-500 kg N ha yr). From 2000 to 2005, plots received 0, 20, 40, or 80 kg P ha yr and 250 kg N ha yr; from 2005 to 2010, no P fertilizer was applied to any plots. In 2005, soil P pool concentrations at the highest P fertilization rates were significantly elevated compared with those in 2000 but had decreased to 2000 concentrations by 2010. In soils receiving no P, soil P pool concentrations were significantly lower than those in 1994 only in 2010. There were few changes in P forms determined by P-NMR. Orthophosphate followed the same trend observed for the soil P pools; total organic P, total inositol phosphates, and total orthophosphate monoesters and diesters were highest in 2010 in the soil receiving no P fertilizer for 10 yr. For these soils, fertilizer application and cessation influenced inorganic P more than organic P.

Electron Donor Substances and Iron Oxides Stimulate Anaerobic Dechlorination of DDT in a Slurry System with Hydragric Acrisols.

The interactive effects between electron donor substances and iron (Fe) oxides have significant influence on electron transfer and the growth of Fe-reducing bacteria, which may affect the reductive dechlorination of 1,1,1-trichoro-2,2-bis(p-chlorophenyl)ethane (DDT) in soils. To evaluate the roles of volatile fatty acids and Fe(III) oxide in accelerating the reductive dechlorination of DDT in Hydragric Acrisols, a batch anaerobic incubation experiment was conducted in a slurry system with the following seven treatments: sterile soil, control (DDT-contaminated soil), lactic acid, propionic acid, goethite, lactic acid + goethite, and propionic acid + goethite. Results showed that after 20 d of incubation, DDT residues for these treatments decreased by 34, 65, 77, 81, 77, 90, and 92% of the initial quantities, respectively, with 1,1-dichloro-2,2-bis(4-chlorophenyl)-ethane as the dominant metabolite. The application of lactic acid had no significant effect on DDT dechlorination in the first 8 d while the methanogenesis rate increased quickly but accelerated DDT dechlorination after Day 8 while the methanogenesis rate decreased and Fe(II) contents increased. The application of propionic acid enhanced DDT dechlorination rates throughout the incubation. The amendment by goethite stimulated microbial reduction of Fe(III) oxides to generate Fe(II), which was an efficient electron donor, thus accelerating DDT dechlorination significantly in the early incubation period. A synergetic interaction that accelerated DDT dechlorination, either between lactic acid and goethite or between propionic acid and goethite, was obtained. The results will be of great significance to develop efficient in situ remediation technology of DDT-contaminated soil.

Characterization of Organic Phosphorus Form and Bioavailability in Lake Sediments using P Nuclear Magnetic Resonance and Enzymatic Hydrolysis.

Lake sediments are known to be a significant source of phosphorus (P) to plankton populations under certain biogeochemical conditions; however, the contribution of sediment organic P (P) to internal P loads remains poorly understood. We investigated P speciation and bioavailability in sediments collected over multiple months from a shallow, eutrophic bay in Lake Champlain (Missisquoi Bay, VT) using solution P nuclear magnetic resonance (NMR) spectroscopy and enzymatic hydrolysis (EH) analysis of sediments collected during years with (2008) and without (2007) algal blooms. Sediments collected during bloom onset (July) and peak bloom (August) months contained the largest proportion of enzyme-labile P, whereas pre- and postbloom sediments were primarily composed of nonlabile P. Monoester P to diester P ratios changed with respect to depth, particularly during bloom periods. Monoester P and DNA accumulation, likely from settling particulate matter, began at the onset of the bloom and continued into October 2008 during the postbloom period. The disappearance of inositol hexakisphosphate stereoisomers and the generation of orthophosphate at lower sediment depths was also evident in August 2008. Principal components analysis of EH and NMR species proportions confirmed differences between sediment cores collected during bloom onset and peak bloom, compared with pre- and postbloom sediments. Large enzyme-labile and P species proportions corresponded to increased sediment P flux and reduced manganese and iron species in porewater. These findings suggest that interseasonal changes in P speciation may influence P mobility in sediments and contribute to important feedback dynamics between biological productivity and sediment water interface geochemistry.

Investigation of soil legacy phosphorus transformation in long-term agricultural fields using sequential fractionation, P K-edge XANES and solution P NMR spectroscopy.

Understanding legacy phosphorus (P) build-up and draw-down from long-term fertilization is essential for effective P management. Using replicated plots from Saskatchewan, Canada, with P fertilization from 1967 to 1995 followed by either P fertilization or P cessation (1995-2010), soil P was characterized in surface and subsurface layers using sequential fractionation, P K-edge X-ray absorption near-edge structure (XANES) and solution (31)P nuclear magnetic resonance (P NMR) spectroscopy. Legacy P from a 28-year build-up was sufficient for 15 years of wheat cultivation, resulting in no significant differences in crop yield in 2010. In surface soils, soil test (Olsen) P decreased significantly in unfertilized plots compared with 1995, which was reflected in declining aluminum (hydr)oxide-associated inorganic P by fractionation and XANES. Furthermore, XANES analysis revealed a decrease of calcium-associated P in 2010-unfertilized soils at both depths and an increase of Fe (hydr)oxides-associated P in the 2010-fertilized and -unfertilized surface soils relative to the 1995 soils. Increased total organic P and orthophosphate diesters by P NMR and accumulated inositol hexaphosphate by XANES were observed in surface soils with P fertilization cessation. In subsurface soils, few legacy P transformations were detected. These results provide important information about legacy P to improve agricultural sustainability while mitigating water quality deterioration.

Phosphorus speciation in a eutrophic lake by ³¹P NMR spectroscopy.

For eutrophic lakes, patterns of phosphorus (P) measured by standard methods are well documented but provide little information about the components comprising standard operational definitions. Dissolved P (DP) and particulate P (PP) represents important but rarely characterized nutrient pools. Samples from Lake Mendota, Wisconsin, USA were characterized using 31-phosphorus nuclear magnetic resonance spectroscopy ((31)P NMR) during the open water season of 2011 in this unmatched temporal study of aquatic P dynamics. A suite of organic and inorganic P forms was detected in both dissolved and particulate fractions: orthophosphate, orthophosphate monoesters, orthophosphate diesters, pyrophosphate, polyphosphate, and phosphonates. Through time, phytoplankton biomass, temperature, dissolved oxygen, and water clarity were correlated with changes in the relative proportion of P fractions. Particulate P can be used as a proxy for phytoplankton-bound P, and in this study, a high proportion of polyphosphate within particulate samples suggested P should not be a limiting factor for the dominant primary producers, cyanobacteria. Hypolimnetic particulate P samples were more variable in composition than surface samples, potentially due to varying production and transport of sinking particles. Surface dissolved samples contained less P than particulate samples, and were typically dominated by orthophosphate, but also contained monoester, diester, polyphosphate, pyrophosphate, and phosphonate. Hydrologic inflows to the lake contained more orthophosphate and orthophosphate monoesters than in-lake samples, indicating transformation of P from inflowing waters. This time series explores trends of a highly regulated nutrient in the context of other water quality metrics (chlorophyll, mixing regime, and clarity), and gives insight on the variability of the structure and occurrence of P-containing compounds in light of the phosphorus-limited paradigm.

Long-term impact of tillage practices and phosphorus fertilization on soil phosphorus forms as determined by p nuclear magnetic resonance spectroscopy.

Conservation tillage practices have become increasingly common in recent years to reduce soil erosion, improve water conservation, and increase soil organic matter. Research suggests that conservation tillage can stratify soil test phosphorus (P), but little is known about the effects on soil organic P. This study was conducted to assess the long-term effects of tillage practices (no-till [NT] and mouldboard plowing) and P fertilization (0 and 35 kg P ha) on the distribution of P species in the soil profile. Soil samples from a long-term corn-soybean rotation experiment in Québec, Canada, were collected from three depths (0-5, 5-10, and 10-20 cm). These samples were analyzed for total P (TP), total C (TC), total N (TN), pH, and Mehlich-3 P (PM3); P forms were characterized with solution phosphorus-31 nuclear magnetic resonance spectroscopy (P-NMR). Results showed a stratification of TP, TC, TN, pH, PM3, and Mehlich-3-extractable aluminum and magnesium under NT management. The PM3 and orthophosphate concentrations were greater at the soil surface (0-5 cm) of the NT-P (soil treatment with 35 kg P ha) treatment. Organic P forms (orthophosphate monoesters, especially -IP, and nucleotides) had accumulated in the deep layer of NT treatment possibly due to preferential movement. We found evidence that the NT system and P fertilization changed the distribution of P forms along the soil profile, potentially increasing soluble inorganic P loss in surface runoff and organic P in drainage and decreasing bioavailability of inorganic and organic P in deeper soil layers.

Complementary Phosphorus Speciation in Agricultural Soils by Sequential Fractionation, Solution P Nuclear Magnetic Resonance, and Phosphorus K-edge X-ray Absorption Near-Edge Structure Spectroscopy.

Ultisols in China need phosphorus (P) fertilization to sustain crop production but are prone to P loss in runoff. Balancing P inputs and loss requires detailed information about soil P forms because P speciation influences P cycling. Analytical methods vary in the information they provide on P speciation; thus, we used sequential fractionation (SF), solution P nuclear magnetic resonance (P-NMR), and P K-edge X-ray absorption near-edge structure (XANES) spectroscopy to investigate organic P (P) and inorganic P (P) species in Chinese Ultisols managed for different crops and with different fertilizer inputs in the first study to combine these techniques to characterize soil P. Sequential fractionation showed that moderately labile NaOH-P was the largest P pool in these soils, P varied from 20 to 47%, and residual P ranged from 9 to 31%. Deoxyribonucleic acid (1-5%) and -inositol hexakisphosphate (-IHP, 4-10%) were the major P forms from P-NMR. Orthophosphate diesters determined by NMR were significantly correlated with labile NaHCO-P in SF ( > 0.981; < 0.001). Soil P was shown to be predominantly associated with iron and soluble calcium (Ca) by XANES. Furthermore, XANES identified hydroxyapatite in the soil receiving the highest rates of Ca-phosphate fertilizer, which had the highest HCl-P pool by SF, and also identified IHP (7%) in the soil with the highest proportion of -IHP from P-NMR. These results strongly suggest that a combined use of SF, solution P-NMR, and P K-edge XANES spectroscopy will provide the comprehensive information about soil P species needed for effective soil P management.

Phosphorus forms and chemistry in the soil profile under long-term conservation tillage: a phosphorus-31 nuclear magnetic resonance study.

In many regions, conservation tillage has replaced conventional tilling practices to reduce soil erosion, improve water conservation, and increase soil organic matter. However, tillage can have marked effects on soil properties, specifically nutrient redistribution or stratification in the soil profile. The objective of this research was to examine soil phosphorus (P) forms and concentrations in a long-term study comparing conservation tillage (direct drilling, "No Till") and conventional tillage (moldboard plowing to 20 cm depth, "Till") established on a fine sandy loam (Orthic Humo-Ferric Podzol) in Prince Edward Island, Canada. No significant differences in total carbon (C), total nitrogen (N), total P, or total organic P concentrations were detected between the tillage systems at any depth in the 0- to 60-cm depth range analyzed. However, analysis with phosphorus-31 nuclear magnetic resonance spectroscopy showed differences in P forms in the plow layer. In particular, the concentration of orthophosphate was significantly higher under No Till than Till at 5 to 10 cm, but the reverse was true at 10 to 20 cm. Mehlich 3-extractable P was also significantly higher in No Till at 5 to 10 cm and significantly higher in Till at 20 to 30 cm. This P stratification appears to be caused by a lack of mixing of applied fertilizer in No Till because the same trends were observed for pH and Mehlich 3-extractable Ca (significantly higher in the Till treatment at 20 to 30 cm), reflecting mixing of applied lime. The P saturation ratio was significantly higher under No Till at 0 to 5 cm and exceeded the recommended limits, suggesting that P stratification under No Till had increased the potential for P loss in runoff from these sites.