Solution 31P Nuclear Magnetic Resonance Research Articles

Intracellular polyphosphate length characterization in polyphosphate accumulating microorganisms (PAOs): Implications in PAO phenotypic diversity and enhanced biological phosphorus removal performance

Polyphosphate (polyP) accumulating organisms (PAOs) are the key agent to perform enhanced biological phosphorus removal (EBPR) activity, and intracellular polyP plays a key role in this process. Potential associations between EBPR performance and the polyP structure have been suggested, but are yet to be extensively investigated, mainly due to the lack of established methods for polyP characterization in the EBPR system. In this study, we explored and demonstrated that single-cell Raman spectroscopy (SCRS) can be employed for characterizing intracellular polyPs of PAOs in complex environmental samples such as EBPR systems. The results, for the first time, revealed distinct distribution patterns of polyP length (as Raman peak position) in PAOs in lab-scale EBPR reactors that were dominated with different PAO types, as well as among different full-scale EBPR systems with varying configurations. Furthermore, SCRS revealed distinctive polyP composition/features among PAO phenotypic sub-groups, which are likely associated with phylogenetic and/or phenotypic diversity in EBPR communities, highlighting the possible resolving power of SCRS at the microdiversity level. To validate the observed polyP length variations via SCRS, we also performed and compared bulk polyP length characteristics in EBPR biomass using conventional polyacrylamide gel electrophoresis (PAGE) and solution 31P nuclear magnetic resonance (31P-NMR) methods. The results are consistent with the SCRS findings and confirmed the variations in the polyP lengths among different EBPR systems. Compared to conventional methods, SCRS exhibited advantages as compared to conventional methods, including the ability to characterize in situ the intracellular polyPs at subcellular resolution in a label-free and non-destructive way, and the capability to capture subtle and detailed biochemical fingerprints of cells for phenotypic classification. SCRS also has recognized limitations in comparison with 31P-NMR and PAGE, such as the inability to quantitatively detect the average polyP chain length and its distribution. The results provided initial evidence for the potential of SCRS-enabled polyP characterization as an alternative and complementary microbial community phenotyping method to facilitate the phenotype-function (performance) relationship deduction in EBPR systems.

Phosphorus mineralization affected by urea in an intensively managed agricultural soil

AbstractA mineralizable P fractionin soils has not been considered in the current agronomic soil P test. Organic P might be a potential source of bioavailable P under the influence of specific soil conditions such as N input. In this laboratory incubation study, the effects of urea (0.1–0.3 g N kg–1 soil) on P mineralization was investigated in an intensively managed agricultural soil using chemical extractions, phosphatase activity analysis, and solution 31P nuclear magnetic resonance spectroscopy (NMR). All urea application rates stimulated P release and P mineralization after 5 d, and bioavailable P increased for up to 40 d. The result of NMR analysis and phosphatase activity supported a shift from organic P to orthophosphate. Urea applications generally increased labile P from ∼5 to ∼24 μg g–1. However, acidity generated from the oxidation of NH4+ under the highest urea treatment (0.3 g of N kg–1 soil) suppressed P mineralization, indicating the degree of urea application rate is sensitive to P mineralization. The results suggested the use of urea could enhance P bioavailability in P‐rich agricultural soils. Tapping into reusable organic P resources in soils might be one of the practical and conservative approaches in the current agriculture.

A new solution 31P NMR sample extraction scheme for freshwater ecosystem sediments.

A new approach for the extraction of organic phosphorus (Po) from freshwater sediments, which can be used in solution 31P nuclear magnetic resonance spectroscopy (31P NMR), has been developed and optimized. This approach addresses three important factors for sediment extraction: pH, organic matter (OM), and paramagnetic ions. We classified the sediments according to the pH, OM, and paramagnetic ions (acidic: pH < 7, alkaline: pH > 7; low OM: OM < 100 g·kg-1, high OM: OM > 100 g·kg-1; non-calcareous: Ca/(Fe + Al) < 0.5, calcareous: Ca/(Fe + Al) > 0.5). The 0.25 and 0.5 mol·L-1 NaOH were optimum concentration for acidic and alkaline sediment extracted, respectively. The ratio of sediment to extraction remains at 1:10 (w:v) which exhibited higher extraction efficiency compared with 1:5 and 1:20 for both low and high OM sediments. Use of 25 mmol·L-1 and 50 mmol·L-1 ethylenediaminetetraacetic acid (EDTA) was optimal for Po extraction from non-calcareous and calcareous sediments, respectively. A useful extraction ratio table was developed through systematic orthogonal experiment. This new approach will allow 31P NMR to be more efficiently used for freshwater Po analysis and will help answer questions regarding to the fate and function of Po in freshwater sediments.

Phosphorus compounds in the dissolved and particulate phases in urban rivers and a downstream eutrophic lake as analyzed using 31P NMR

Phosphorus (P) discharges from human activities result in eutrophication of lakes. We investigated whether the forms of phosphorus (P) in rivers with high effluent loads flowing through urban areas of Sapporo, Japan, were transformed when transported downstream into a eutrophic lake, namely Lake Barato. We hypothesized that the inorganic P supplied from the rivers might be transformed to organic forms in the lake. The results showed that soluble reactive phosphorus (SRP) and particulate inorganic phosphorus (PIP) dominated in the river discharge to the lake. Suspended solids in the rivers were rich in iron (Fe) so PIP was associated with Fe. A comparison of the concentrations at the river mouth and 4.5 km downstream showed that the concentrations of SRP and PIP were lower at 4.5 km downstream than at the river mouth, whereas the concentrations of organic P (i.e., dissolved organic phosphorus and particulate organic phosphorus) were similar. The results from solution 31P nuclear magnetic resonance spectroscopy of lake water showed that pyrophosphate was only present in the particulate fraction, while orthophosphate diesters (DNA-P) were only present in the dissolved fraction. Riverine samples contained orthophosphate (ortho-P) only, while lake samples contained ortho-P, orthophosphate monoesters, and DNA-P. The results suggest that the P forms, particularly those of dissolved P, shifted from inorganic to organic forms as the water was discharged from the river to the lake.

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 (0-10cm) 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.

Long-term changes in land use influence phosphorus concentrations, speciation, and cycling within subtropical soils

While land conversion from native vegetation to agriculture influences the concentration, speciation, and cycling of soil phosphorus (P), the nature of these changes remain poorly understood. We collected surface soils (0–10 cm) from paired sites at three locations, comparing soil from native vegetation with adjacent soils converted for cropping, pasture, and plantation for up to 115 y. The extent of organic P loss upon land use change differed between the three soils, with conversion to cropping causing the largest decreased in soil organic P as well as phosphatase activity. Using solution 31P nuclear magnetic resonance (NMR), it was found that cropping caused a pronounced decrease in organic P – both orthophosphate monoesters and orthophosphate diesters. Furthermore, cropping soils had a substantial reduction in the diester-P/monoester-P ratio, indicating the preferential degradation of the more labile orthophosphate diester-P upon conversion to cropping. Importantly, by subsequently converting cropping land to pasture or plantation, these adverse P-related changes could be reversed or at least halted. Synchrotron-based X-ray absorption near-edge structure (XANES) demonstrated that land use change had no pronounced impact on inorganic P, with sorbed P dominating in all treatments. Changes in land use also influenced bacterial diversity, with land use change effects being specific to the three soils. This study provides information on how land use changes alters P behaviour and cycling in soils, with this being important for ensuring the sustainable use of soils for food production.

Phosphorus forms in the sediment of seagrass meadows affected mainly by fungi rather than bacteria: a preliminary study based on 31P-NMR and high-throughput sequencing

Abstract Microorganisms play an important role in the circulation of phosphorus (P) in the sediment of coastal wetland ecosystems. In this study, solution 31P nuclear magnetic resonance (NMR) was used to determine different forms of P in the sediments of four different seagrass meadows and a bare tidal flat, while high-throughput 16S and ITS rRNA gene sequencing was used to determine the microbial community composition. The solution 31P-NMR spectra revealed six forms of the P compounds detected by the NaOH-EDTA extraction of sediments, where Ortho-P was the most dominant P compound, followed by Mono-P. The Po compounds were more varied in the seagrass meadow sediments and more abundant compared to the bare tidal flat. Bacterial communities in the sediments collected from E. acoroides and fungal communities in the bare tidal flat were relatively different from those at the other sites. The relative abundance of P-cycling-related fungi belonging to the phylum Ascomycota was 26.20% and was much higher than that of bacteria (only 0.29%) belonging to the class Bacilli. Mono-P was the major factor determining the distribution of P-cycling-related fungi and negatively correlated with the relative abundance of Aspergillus and Trichoderma. We believe that fungi can affect P forms in the sediment of seagrass meadows more than bacteria.

Identification of lower-order inositol phosphates (IP&amp;lt;sub&amp;gt;5&amp;lt;/sub&amp;gt; and IP&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt;) in soil extracts as determined by hypobromite oxidation and solution &amp;lt;sup&amp;gt;31&amp;lt;/sup&amp;gt;P NMR spectroscopy

Abstract. Inositol phosphates (IPs) are a major pool of identifiable organic phosphorus (P) in soil. However, insight into their distribution and cycling in soil remains limited, particularly of lower-order IP (IP5 and IP4). This is because the quantification of lower-order IP typically requires a series of chemical extractions, including hypobromite oxidation to isolate IP, followed by chromatographic separation. Here, for the first time, we identify the chemical nature of organic P in four soil extracts following hypobromite oxidation using solution 31P NMR spectroscopy and transverse relaxation (T2) experiments. Soil samples analysed include A horizons from a Ferralsol (Colombia), a Cambisol and a Gleysol from Switzerland, and a Cambisol from Germany. Solution 31P nuclear magnetic resonance (NMR) spectra of the phosphomonoester region in soil extracts following hypobromite oxidation revealed an increase in the number of sharp signals (up to 70) and an on average 2-fold decrease in the concentration of the broad signal compared to the untreated soil extracts. We identified the presence of four stereoisomers of IP6, four stereoisomers of IP5, and scyllo-IP4. We also identified for the first time two isomers of myo-IP5 in soil extracts: myo-(1,2,4,5,6)-IP5 and myo-(1,3,4,5,6)-IP5. Concentrations of total IP ranged from 1.4 to 159.3 mg P per kg soil across all soils, of which between 9 % and 50 % were comprised of lower-order IP. Furthermore, we found that the T2 times, which are considered to be inversely related to the tumbling of a molecule in solution and hence its molecular size, were significantly shorter for the underlying broad signal compared to for the sharp signals (IP6) in soil extracts following hypobromite oxidation. In summary, we demonstrate the presence of a plethora of organic P compounds in soil extracts, largely attributed to IPs of various orders, and provide new insight into the chemical stability of complex forms of organic P associated with soil organic matter.

Soil Phosphorus Dynamics Across a Holocene Chronosequence of Aeolian Sand Dunes in a Hypermaritime Environment on Calvert Island, BC, Canada

Phosphorus (P) is an essential nutrient for plant growth, but soil P concentrations decline with increasing soil age. Phosphorus often limits tree growth within the hypermaritime Coastal Western Hemlock zone in British Columbia, Canada, particularly where parent material with low P concentrations have experienced rapid weathering. To sustainably manage forests in this region, more information is needed about changes in soil P concentrations and dynamics that occur with time. This study characterized the forms and abundance of soil and foliar P compounds using a soil chronosequence developed on aeolian sand dunes on Calvert Island and compared results to chronosequences in other locations. Eight time points were examined, from a modern foredune to a relict, stabilized dune (~10,760 years old). Soil horizons were analyzed for bulk density, pH, and concentrations of total carbon (C), nitrogen (N) and total P (TP), iron (Fe) and aluminum (Al), total organic P (Po), and Mehlich-extractable P and cations. For each site, P forms in L, H and organically-enriched mineral (M) horizons were characterized with solution 31P nuclear magnetic resonance spectroscopy (P-NMR), as were foliar samples from tree species spanning all age classes except the youngest dune. This chronosequence followed the Walker and Syers (1976) model, with an exponential decline in TP mass and a humped-shape curve in Po mass with increasing age. The L horizon had lower TP concentrations than foliage samples, but similar P forms. The H horizons had a greater proportion of DNA, phosphonates and nucleotides than the L horizon and increased proportions of myo- and scyllo-inositol hexakisphosphate (IHP) with increasing age. The mineral horizons had much lower TP concentrations than other horizons and increased proportions of IHP and DNA with increasing age, which were correlated to increased exchangeable and amorphous Al concentrations. In all sample types, the proportion of orthophosphate declined with increasing age. These results enhance knowledge of P cycling within hypermaritime soils, particularly the P decline that will occur with age. This will aid in the sustainable management of the low-productivity forests typical of these ecosystems.

Dynamics of phosphorus composition in suspended particulate matter from a turbid eutrophic shallow lake (Lake Chaohu, China): Implications for phosphorus cycling and management

Particulate phosphorus (P) dominates the total P (TP) content in lacustrine water columns and is a primary source of dissolved P in turbid eutrophic shallow lakes. However, the spatiotemporal variability of P compositions in suspended particulate matter (SPM) remains poorly understood. In this study, we applied chemical extraction and solution 31P nuclear magnetic resonance (31P NMR) to assess the seasonal variations of SPM P compositions from a shallow turbid lake (Lake Chaohu, China) and its main river tributaries. P fractionation analysis indicated that mobile P (the sum of labile-P, iron-bound P, and organic P) accounted for >60% of the TP in SPM and showed high spatiotemporal variability throughout the year-long field investigation. In most seasons, riverine SPM (in urban rivers or rivers with high flow) contained a higher mobile P content than that of the lake and was therefore a dominant source of lacustrine mobile particulate P. Solution 31P NMR identified five types of P compounds in SPM, with highest contributions from orthophosphate. Organic P components and concentrations showed high seasonal variability, and elevated p values occurred during the summer algal bloom. The correlation analysis between organic and inorganic P fractions inferred the possible degradation of organic P into reactive inorganic components of SPM. Consequently, biological or chemical processes would further transform the labile inorganic P into soluble reactive phosphorus, which is readily utilized by lacustrine algae. Our results suggest that the labile forms of P in SPM were highly dynamic and significantly contributed to the eutrophication of the turbid shallow lake.

Composition characterization and biotransformation of dissolved, particulate and algae organic phosphorus in eutrophic lakes

Characteristics and transformation of organic phosphorus in water are vital to biogeochemical cycling of phosphorus and support of blooms of phytoplankton and cyanobacteria. Using solution 31P nuclear magnetic resonance (NMR), combined with field surveys and lab analyses, composition and structural characteristics of dissolved phosphorus (DP), particulate phosphorus (PP) and organic P in algae were studied in two eutrophic lakes in China, Tai Lake and Chao Lake. Factors influencing migration and transformation of these constituents in lake ecosystems were also investigated. A method was developed to extract, flocculate and concentrate DP and PP from lake water samples. Results showed that orthophosphate (Ortho-P) constituted 32.4%–81.3% of DP and 43.7%–54.9% of PP, respectively; while monoester phosphorus (Mono-P) was 13.2%–54.0% of DP and 32.9%–43.7% of PP, respectively. Phosphorus in algae was mostly organic P, especially Mono-P, which was ≥50% of TP. Environmental factors and water quality parameters such as temperature (T), electrical conductivity (EC), pH, secchi depth (SD), dissolved oxygen (DO), chemical oxygen demand (CODcr), chlorophyll-a (Chl-a), affected the absolute and relative concentrations of various P components in the two lakes. Increased temperature promoted bioavailable P (Ortho-P and Mono-P) release to the lake waters. The results can provide an important theoretical basis for the mutual conversion process of organic P components between various media in the lake water environment.

Improvement of quantitative solution 31P NMR analysis of soil organic P: a study of spin\u2013lattice relaxation responding to paramagnetic ions

Solution 31P nuclear magnetic resonance (NMR) spectroscopy has been widely applied to analyze the speciation of soil organic P; however, this time-consuming technique suffers from a low analytical efficiency, because of the lack of fundamental information such as the spin–lattice relaxation (T1) of 31P nucleus for model P compounds. In this study, we for the first time determined the T1 values of twelve typical soil organic P compounds using the inversion recovery method. Furthermore, we examined the effect of co-existing paramagnetic ions (e.g., Fe3+ and Mn2+) on the reduction of the T1 values of these compounds. Without the addition of paramagnetic ions, the T1 values of twelve model P compounds ranged from 0.61 s for phytic acid to 9.65 s for orthophosphate. In contrast, the presence of paramagnetic ion significantly shortened the T1 values of orthophosphate, pyrophosphate, and phytic acid to 1.29, 1.26, and 0.07 s, respectively, except that of deoxyribonucleic acid (DNA) remaining unchanged. Additionally, we evaluated the feasibility of improving the efficiency of quantitative 31P NMR analysis via addition of paramagnetic ion. Results show that, after an addition of 50 mg L−1 paramagnetic ions, 31P NMR measurement can be 3 times more efficient, attributed to the reduced T1 and the corresponding recycle delay.

Phosphorus Speciation in Long-Term Drained and Rewetted Peatlands of Northern Germany

Previous studies, conducted at the inception of rewetting degraded peatlands, reported that rewetting increased phosphorus (P) mobilization but long-term effects of rewetting on the soil P status are unknown. The objectives of this study were to (i) characterize P in the surface and subsurface horizons of long-term drained and rewetted percolation mires, forest, and coastal peatlands and (ii) examine the influence of drainage and rewetting on P speciation and distributions using wet-chemical and advanced spectroscopic analyses. The total P was significantly (p &lt; 0.05) different at the surface horizons. The total concentration of P ranged from 1022 to 2320 mg kg−1 in the surface horizons and decreased by a factor of two to five to the deepest horizons. Results of the chemical, solution 31P nuclear magnetic resonance (NMR), and P K-edge X-ray absorption near-edge structure (XANES) indicated that the major proportions of total P were organic P (Po). In the same peatland types, the relative proportions of Po and stable P fractions were lower in the drained than in the rewetted peatland. The results indicate that long-term rewetting not only locks P in organic matter but also transforms labile P to stable P fractions at the surface horizons of the different peatland types.

Soil phosphorus pools with addition of fertiliser phosphorus in a long-term grazing experiment

Grasslands are a globally important use of land for food and fibre production, which often require the addition of phosphorus (P) fertiliser to maximise plant production. However, a large proportion of the added P can accumulate in pools of poorly available inorganic and organic P in the surface soil layer under grasslands. The aim of this study was to identify the chemical nature of the organic P in soils from a long-term fertiliser by grazing permanent pasture experiment that have received varying additions of phosphatic fertiliser (cumulative P input of 27, 169, 311, 513, 745 and 1035 kg P ha−1) over a period of 37 years. The design of the experiment uniquely provides insight into the response of soil organic P to the addition of fertiliser P on the decadal scale. On average, 46% of the added fertiliser P was recovered as total P in the 0–100 mm soil layer after 37 years of phosphate addition. The content of both inorganic and organic forms of soil P increased with the addition of fertiliser P. The accumulation of organic P increased linearly up to a cumulative P input of 745 kg P ha−1 and plateaued thereafter. The majority of organic P in all treatments was detected as a broad signal in the phosphomonoester region of solution 31P nuclear magnetic resonance (NMR) spectra; this also accounted for 79% of the accumulated organic P in fertilised soil. Our results indicate that accumulation of P in the organic portion as complex forms eventually reaches a new equilibrium where no net accumulation would be expected with further addition of phosphate.

Soil phosphorus changes in a grey desert soil in Xinjiang, China, using 31P nuclear magnetic resonance spectroscopy

This study investigated the effects of different long-term fertilization regimes on the total phosphorus (TP) content and the phosphorus (P) composition of grey desert soil in Xinjiang, China, and clarified the variation in P content under different long-term fertilization regimes. Solution 31P nuclear magnetic resonance spectroscopy (31P NMR) was used to analyze the variation in TP and P composition under different long-term fertilization regimes. The results showed that phosphate monoester was the major form of P and that no other forms of soil organic P (OP) were detected in grey desert soil, Xinjiang, China.

Characteristics of organic phosphorus fractions in soil from water-level fluctuation zone by solution 31P-nuclear magnetic resonance and enzymatic hydrolysis

Phosphorus (P) is an essential nutrient element for biological growth that can contribute to eutrophication in aquatic ecosystems. Water trophic status and algae growth are primarily related to the content of bioavailable P, which is primarily related to enzymatically hydrolysable organic P(EHOP) and dissolved inorganic P(IP). In this study, soil samples from the water-level fluctuation zone (WLFZ) were collected from a tributary of the Three Gorges Reservoir (TGR) to characterize the properties of organic P(OP) fractions using solution 31P-nuclear magnetic resonance (NMR) and enzymatic hydrolysis. 31P-NMR showed that orthophosphate was the main part of the bioavailable P in the WLFZ soil and accounted for 80.4% of the NaOH-EDTA extractable total P (NaOH-EDTA TP), while phosphate monoester accounted for 60.5% of NaOH-EDTA extractable OP (NaOH-EDTA OP). The soil properties and replenishment from the mainstream of the Yangtze River to the Pengxi River have a certain effect on the content and distribution of P forms in the WLFZ soil of the tributary. The EHOP accounted for 28.1% of the NaOH-EDTA OP, and a significant positive correlation was observed between labile monoester P and EHOP and organic matter (OM). The water-soluble OP(H2O-OP), bicarbonate-extractable OP(NaHCO3-OP), and Fe- and Al-associated OP(Fe/Al-OP) were significantly hydrolyzed by phosphatase and thus exhibited great release potential. The ranking of the bioavailability of OP was Fe/Al-OP > H2O-OP > NaHCO3-OP. Phytate-like P were mainly found in H2O-OP and NaHCO3-OP, which indicated that periodic submersion–emersion cycles promoted the release of phytate-like P from Fe/Al-OP into the water column of the TGR. These observations suggest that when the external P input was effectively controlled, a huge risk of release of the internal OP from the WLFZ soil, and the biogeochemical cycling of the bioavailable P played an important role in maintaining the eutrophication of the reservoir.

Influence of long-term phosphorus fertilisation history on the availability and chemical nature of soil phosphorus

Data on the dynamics and fate of phosphorus (P) under low soil-test P (STP) conditions is essential for the development of cropping strategies with a high P use efficiency. This study examined the effects of long-term (20 years) mineral and organic fertiliser P applications on a P-depleted sandy loam soil in Denmark. The cycling of P was examined by use of P budgets (inputs-offtake), chemical P extractions, 33P isotopic exchange kinetics (IEK), and solution 31P nuclear magnetic resonance (NMR) spectroscopy on NaOH-EDTA extracts.Recovery of applied P in the topsoil was smaller for animal slurry P compared with mineral fertiliser P. The budgets suggest deeper soil layers play an important role for the cycling of P. Resin-extractable P (2 to 17 mg kg−1), Olsen-P (7 to 16 mg kg−1) and E1min (1 to 6 mg kg−1) were correlated with the P budgets. Between 63 and 77% of total inorganic P was not exchangeable in a period of three months (E>3months), with the lowest value observed in no-P treatment N1K1. The data show that a redistribution of exchangeable P had taken place under the influence of a strongly negative P budget. Microbial P (6 to 18 mg kg−1) increased under animal slurry inputs compared with mineral fertiliser applications (p < 0.05). All soils were dominated by phosphomonoesters and orthophosphate (98 to 99% of the NMR signal). Concentrations of orthophosphate (86 to 135 mg kg−1) varied significantly between treatments (p < 0.01), whereas forms of organic P remained largely unchanged.The results demonstrate that P applications increased the amount of P that is potentially available for plants, irrespective of input form. Nevertheless, most P applied in excess of crop uptake resulted in an increase of the amount of P that is slowly exchangeable. Under low soil test P conditions such as in the current trial, fertiliser P applied in excess of plant demand that accumulates in soil would thus only be partially available for crops in subsequent years. On the other hand the data suggests that soil P reserves may be utilised for crop growth, but at the low soil P intensity plant access to P will have to be managed carefully.

Bioavailability of organic phosphorus in an eutrophic lake: Insights from an in-situ experiment

Abstract The bioavailability of organic phosphorus (Porg) in surface sediments of an eutrophic lake was studied in an in-situ experiment. On the temporal scale, soluble reactive phosphorus (SRP) in the surface water showed an initial decrease and then increased in western and middle parts of the lake. In contrast, the SRP remained about 0.22 mg L−1 throughout the year in the eastern area of the lake. Four Porg compounds, phosphonate, orthophosphate monoesters, phospholipids and deoxyribonucleic acid phosphorus, were detected using solution 31P nuclear magnetic resonance spectroscopy. Orthophosphate monoesters were the dominant Porg in the sediment extracts, higher than the orthophosphate diesters deoxyribonucleic acid phosphorus and phospholipids. The SRP and Porg showed obvious seasonal variations in different lake regions. The surface water SRP had a negative relationship with sedimentary Porg in the western and middle lake regions. From spring to autumn, SRP in the water column decreased while Porg in the surface sediment increased; from autumn to winter, SRP in the water column increased and Porg in the surface sediment decreased. According to aquatic metabolism, we inferred that excessive external phosphorus input was the “trigger” and the aquatic plants were the “pump” for Porg biogeochemical cycling in the shallow lake. Therefore, appropriate human intervention, such as the harvest of aquatic plants, is vital for eutrophication control in freshwater ecosystems.

Synthesis, X-ray Crystal Structure, and Photochromism of a Sandwich-Type Mono-Aluminum Complex Composed of Two Tri-Lacunary α-Dawson-Type Polyoxotungstates.

The synthesis and molecular structure of a dimeric, mono-aluminum complex composed of two tri-lacunary α-Dawson polyoxometalates, [H14Al(B-α-P2W15O56)2]7− (1), is described herein. The tetra-n-butylammonium salt of 1, [(n-C4H9)4N]7[H14Al(B-α-P2W15O56)2] (TBA-1) was prepared by passing an aqueous solution of K6[B-α-H3P2W15O59{Al(OH2)}3]⋅14H2O through an ion-exchange resin column (H+-form), followed by addition of tetra-n-butylammonium bromide. Analytically pure and colorless crystals of TBA-1 were obtained via vapor diffusion from acetonitrile/methanol at ~25 °C. Single-crystal X-ray structure analysis revealed that a six-coordinate aluminum ion was sandwiched between two tri-lacunary α-Dawson-type units, resulting in an overall C2h symmetry. The characterization of TBA-1 was accomplished by elemental analyses, thermogravimetric/differential thermal analyses, Fourier-transform infrared spectroscopy, and solution 31P nuclear magnetic resonance spectroscopy. The photochromic properties of TBA-1 were also characterized in methanol under light irradiation (λ = 365 nm and ≥400 nm).

Characterization of fluvo-aquic soil phosphorus affected by long-term fertilization using solution 31P NMR spectroscopy.

Reducing the applications of mineral phosphorus (P) fertilizers and supplementing them by organic fertilizers is becoming a necessary practice in the North China Plain due to overuse of mineral P fertilizers and improper disposal of organic wastes. Knowledge is needed about how the long-term substitution of mineral fertilizers by organic fertilizers affects soil P forms in order to understand soil P transformation and crop P uptake. In this study, we used solution 31P nuclear magnetic resonance (NMR) spectroscopy to characterize P forms in fluvo-aquic soil after 26 years of different fertilization management strategies, organic compost (OM), half compost in combination with half mineral fertilizer NPK (1/2 OM), mineral fertilizer NPK (NPK), mineral fertilizer NK (NK), and an unfertilized control (CK). Results showed that the P extraction efficiency using NaOH-EDTA varied from 13.0 to 27.7% for the soils of the treatments. 31P NMR spectra indicated that the majority of P was in the form of orthophosphate for all the treatments, which constituted 64.3-83.5% of the total extracted P. The application of P fertilizers significantly increased the concentrations of orthophosphate, monoesters and diesters regardless of the P fertilization method, although the proportions of monoesters and diesters were higher in CK. The proportions and concentrations of orthophosphate significantly decreased when all mineral fertilizers were replaced by compost. There was no significant difference in the proportions and concentrations of total organic P, corrected monoesters and diesters in NaOH-EDTA extracts of soils among NPK, 1/2OM and OM treatments. Decreasing mineral P fertilizers and partly replacing them by organic fertilizer in fluvo-aquic soil might increase soil test (Olsen) P and crop P uptake through the degradation of applied organic P forms.