In situ, high-resolution imaging of labile phosphorus in sediments of a large eutrophic lake

Understanding the labile status of phosphorus (P) in sediments is crucial for managing a eutrophic lake, but it is hindered by lacking in situ data particularly on a catchment scale. In this study, we for the first time characterized in situ labile P in sediments with the Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) technique at a two-dimensional (2D), submillimeter resolution in a large eutrophic lake (Lake Taihu, China, with an area of 2338km²). The concentration of DGT-labile P in the sediment profiles showed strong variation mostly ranging from 0.01 to 0.35mgL^-1 with a considerable number of hotspots. The horizontal heterogeneity index of labile P varied from 0.04 to 4.5. High values appeared at the depths of 0-30mm, likely reflecting an active layer of labile P under the sediment-water interface (SWI). Concentration gradients of labile P were observed from the high-resolution 1D DGT profiles in both the sediment and overlying water layers close to the SWI. The apparent diffusion flux of P across the SWI was calculated between -21 and 65ngcm^-2d^-1, which showed that the sediments tended to be a source and sink of overlying water P in the algal- and macrophyte-dominated regions, respectively. The DGT-labile P in the 0-30mm active layer showed a better correlation with overlying water P than the labile P measured by ex situ chemical extraction methods. It implies that in situ, high-resolution profiling of labile P with DGT is a more reliable approach and will significantly extend our ability in in situ monitoring of the labile status of P in sediments in the field.

Distribution of nitrogen and phosphorus in sediment cores and overlying water of Donghu Lake

In this study, the seasonal, vertical distribution of various phosphorus and nitrogen forms in the sediment and overlying water of Donghu Lake were investigated. The concentration of total nitrogen (TN) in overlying water was high in spring and autumn, but that of NO3--N reached its peak in autumn. From summer to autumn and from winter to spring, the concentration of phosphorus in overlying water decreased, while it increased from autumn to winter. Vertical characteristic forms of phosphorus in sediment cores are total phosphorus (TP), labile phosphorus (LP), Fe-P and Al-P, obviously enriched in the surface layer (0-10 cm), but their concentrations are observably reduced along with the depth of sediment. The research is of important theoretical and practical value to understand the status and to control the developmental trend of eutrophication in Donghu Lake.

The research of phosphorus of Xiangxi River nearby the Three Gorges, China

The Xiangxi River is the first middling tributary of the Changjiang River near the Three Gorges Dam. The River is subject to phosphorus pollution mainly from industrial wastewater. As the water quality of the Xiangxi River could directly influence the water quality of the Three Gorges Reservoir, the research on phosphorus levels and its change in the sediment profile of the Xiangxi River could provide useful information in the dynamic changes in the system, thereby offering options for mitigative measures. Water and sediment samples from lower reaches of Xiangxi River were collected and the different forms of phosphorus in sediments of the Xiangxi River were studied. The concentrations of total phosphorus in sediment ranged from 757.67 to 1438.54 mg/kg. Inorganic phosphorus concentrations ranged from 684.63 to 1055.58 mg/kg. Phosphorus contamination was serious in some parts of the Xiangxi River. With an average concentration of 635.17 mg/kg, calcium-bound phosphorus is the main form among different inorganic phosphorus forms. Labile phosphorus and iron/aluminum-bound phosphorus measured 3.40, 0.05and 35.28 mg/kg, respectively. The mobilization potential of phosphorus of sediments was studied through adsorption and release experiments. The equilibrium concentration of phosphorus adsorption and release was around 0.1 mg/L. The initial concentrations of phosphorus in the overlying water and the sediments have obvious effect on phosphorus mobilization potential. In addition, the release rate of phosphorus in sediment increased with water depth.

Variations and possible source of potentially available phosphorus in a Chinese shallow eutrophic lake

Surface, overlying, and interstitial waters were collected at monthly intervals at three experimental stations in a shallow Chinese eutrophic lake (Lake Donghu) to assess the occurrence, distribution, and status of UV-sensitive phosphorus compounds (UVSP) and phosphatase hydrolyzable phosphorus (PHP), coupled with kinetics of alkaline phosphatase activity (APA). Orthophosphate (o-P) concentrations were generally the highest at Station 1, where chlorophyll a (chl a) was a function of o-P at temporal scale. The V-max/K-m of APA obtained by Michaelis-Menten approach paralleled the chlorophyll data at two stations. These facts imply that the development of phytoplankton may be attributed to APA induced by PHP. The potentially available UVSP and PHP peaked in interstitial, overlying, and surface water simultaneously sometimes in 1995 to 1996 and 1997 to 1999. It is postulated that they may arise from the bottom. UVSP peaked in interstitial water at the 12-16 cm layers in sediment cores. Moreover, in interstitial water, UV irradiation resulted in an elevated o-P concentration and decreased APA in a timeseries analysis. Therefore, the mechanism that APA involved in the process of photorelease of o-P was not demonstrated. UVSP is most likely a functional group of labile phosphorus distinct from the enzymatic substrate in this shallow eutrophic lake.

Investigating the of Water treatment residuals on Phosphorus mobility derived from biosolid application to Willow coppice

Short rotation willow coppice (SRWC) treatment of biosolids is limited by the oversupply of biosolid derived phosphorus; this can lead to eventual losses of phosphorus to water. Water treatment residuals (WTR), a by-product of potable water treatment, have been identified as a viable soil amendment for mitigation of phosphorus loss. WTR exploit the capacity of internally held aluminium oxide-hydroxide complexes to immobilise labile phosphorus. However indiscriminate additions to plots can result in inadequate control or excessive immobilization of soluble P, leading to crop deficiencies. Four commercially grown common willow (Salix) genotypes (Terra Nova, Endeavour, Resolution and Tora) were grown in soil amended with WTR at five different application rates (0, 10, 25, 50 and 100 tonne ha-1 air-dry basis) in a glasshouse pot experiment. The effects of application rates on plant yields, tissue P concentrations, P uptake and soil labile P availability were measured. Results indicate labile P was reduced with increasing WTR application rates, without any negative agronomic impacts.

Organic compounds from plant extracts and their effect on soil phosphorus availability

O objetivo deste trabalho foi avaliar o efeito de compostos orgânicos de extratos de plantas de seis espécies e da fertilização fosfatada na disponibilidade de fósforo no solo. Tubos de 30 cm de altura e 5 cm de diâmetro foram preenchidos com Latossolo Vermelho-Amarelo. Cada tubo constituiu uma parcela, em delineamento completamente casualizado, em arranjo fatorial 7x2, com quatro repetições. Extratos líquidos de aveia-preta (Avena strigosa), nabo forrageiro (Raphanus sativus), milho (Zea mays), milheto (Pennisetum glaucum), soja (Glycine max), sorgo forrageiro (Sorghum bicolor) e água (testemunha) foram aplicados em cada parcela, com ou sem fertilização com fosfato solúvel. Após sete dias de incubação, amostras de solo foram coletadas em várias profundidades, e foram analisadas as formas lábil, moderadamente lábil e não lábil de fósforo no solo. Houve acúmulo de fósforo inorgânico nas frações lábil e moderadamente lábil do solo, como conseqüência da adição dos extratos de plantas, principalmente na camada superficial (0-5 cm). O nabo forrageiro, com maior concentração de ácido málico e maior conteúdo de P no tecido do que outras espécies, foi o mais eficiente em incrementar a disponibilidade de P no solo.

Contribuições da micorrização e do Aspergillus niger, como solubilizador de fosfato, no crescimento de milho, em diferentes solos

Pós-graduação em Agronomia - FEIS

Aspergillus niger e Glomus clarum incrementam a disponibilidade de fósforo em Latossolos sob Urochloa brizantha

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Disponibilidade de fósforo em solo cultivado com braquiária em rotação com soja

Pós-graduação em Agronomia (Agricultura) - FCA

Tillage and phosphorus management effects on enzyme-labile bioactive phosphorus availability in Cerrado Oxisols

Phosphorus (P) is an essential element in crop nutrition, which can be growth limiting or an environmental contaminant, if present in excess. Tillage practices have a direct effect on the behavior and availability of soil P. Sorption and availability of various P forms were evaluated in an incubation-fractionation study of three soils, a Typic Paleudults (CR soil) and two Cerrado Oxisols (Latossolo Vermelho-Amarelo [LVA] and Latossolo Vermelho [LV]) with distinct biogeochemical characteristics and tillage management history. Phosphate and myo-inositol hexakisphosphate (mIPH) were strongly sorbed by the soils. Maximum adsorption capacities (S(max)) were 2.2-6.9, 3.3-7.8, and 1.6-19.8 mmol kg(-1) for phosphate in the 0-40 cm depths of the CR, LV, and LVA soils, respectively. For mIPH, S. were 1.2-3.7, 3.7-5.5, and 4.6-5.2 mmol kg(-1). Saturation indices reflected the long-term effect of repeated manure applications on the Paleudults and the near saturation of its P holding capacity, in contrast to the recently cultivated Cerrado soils. Tillage method appeared to have altered P retention characteristics of the near-surface zone very slightly, while increases in ligand-exchangeable (EEP;) and enzyme-labile organic P (EDTA-PHP) forms were observed in no-till Oxisols. In the Paleudults, added manure P increased bioactive P fractions and P saturation of no-till near-surface soil zone. Estimates of all bioactive P fractions using the ligand-based enzymatic assay showed it to be an effective method for assessing P availability in soil and developing sustainable P management strategies, particularly in Cerrado Oxisols that were low in organic matter while having an extensive P-fixing capacity. Published by Elsevier B.V.

Phosphorus in agricultural soils of Finland - characterization of reserves and retention in mineral soil profiles

An overwhelming majority of all the research on soil phosphorus (P) has been carried out with soil samples taken from the surface soils only, and our understanding of the forms and the reactions of P at a soil profile scale is based on few observations. In Finland, the interest in studying the P in complete soil profiles has been particularly small because of the lack of tradition in studying soil genesis, morphology, or classification. In this thesis, the P reserves and the retention of orthophosphate phosphorus (PO4-P) were examined in four cultivated mineral soil profiles in Finland (three Inceptisols and one Spodosol). The soils were classified according to the U.S. Soil Taxonomy and soil samples were taken from the genetic horizons in the profiles. The samples were analyzed for total P concentration, Chang and Jackson P fractions, P sorption properties, concentrations of water-extractable P, and for concentrations of oxalate-extractable Al and Fe. Theoretical P sorption capacities and degrees of P saturation were calculated with the data from the oxalate-extractions and the P fractionations. The studied profiles can be divided into sections with clearly differing P characteristics by their master horizons Ap, B and C. The C (or transitional BC) horizons below an approximate depth of 70 cm were dominated by, assumingly apatitic, H2SO4-soluble P. The concentration of total P in the C horizons ranged from 729 to 810 mg kg-1. In the B horizons between the depths of 30 and 70 cm, a significant part of the primary acid-soluble P has been weathered and transformed to secondary P forms. A mean weathering rate of the primary P in the soils was estimated to vary between 230 and 290 g ha-1 year-1. The degrees of P saturation in the B and C horizons were smaller than 7%, and the solubility of PO4-P was negligible. The P conditions in the Ap horizons differed drastically from those in the subsurface horizons. The high concentrations of total P (689-1870 mg kg-1) in the Ap horizons are most likely attributable to long-term cultivation with positive P balances. A significant proportion of the P in the Ap horizons occurred in the NH4F- and NaOH-extractable forms and as organic P. These three P pools, together with the concentrations of oxalate-extractable Al and Fe, seem to control the dynamics of PO4-P in the soils. The degrees of P saturation in the Ap horizons were greater (8-36%) than in the subsurface horizons. This was also reflected in the sorption experiments: Only the Ap horizons were able to maintain elevated PO4-P concentrations in the solution phase − all the subsoil horizons acted as sinks for PO4-P. Most of the available sorption capacity in the soils is located in the B horizons. The results suggest that this capacity could be utilized in reducing the losses of soluble P from excessively fertilized soils by mixing highly sorptive material from the B horizons with the P-enriched surface soil. The drastic differences in the P characteristics observed between adjoining horizons have to be taken into consideration when conducting soil sampling. Sampling of subsoils has to be made according to the genetic horizons or at small depth increments. Otherwise, contrasting materials are likely to be mixed in the same sample; and the results of such samples are not representative of any material present in the studied profile. Air-drying of soil samples was found to alter the results of the sorption experiments and the water extractions. This indicates that the studies on the most labile P forms in soil should be carried out with moist samples.

Phosphorus in suspended matter and sediments of a hypertrophic lake. A case study: Lake Dianchi, China

From June 2004 to December 2004, Lake Dianchi, which had large scale of cyanobacterial blooms was investigated in order to study P-fractionation in the suspended matter and the sediment. The investigation improves our understanding of phosphorus in Lake Dianchi and the relationship between phosphorus and cyanobacterial blooms. It contributes to the available literature on the behavior of P in hypertrophic lakes. The distribution of P-fractions in Lake Dianchi was not uniform from northwest to south, but was closely related to the trophic status of the whole lake. The concentrations of total phosphorus, labile P (NH4Cl-P), Organic P (NaOH-NRP) and loss on ignition in suspended matter were positively correlated with the strength of cyanobacterial blooms. Total phosphorus in suspended matter was relatively stable for almost half an year and closely related to Chl. a concentration. The main content of organic phosphorus is in the cyanobacterial blooms. The concentrations of phosphorus bound to metal oxides and carbonates (NaOH-SRP and HCl-P) in sediment were similar to NaOH-SRP and HCl-P in the corresponding suspended matter. The latter two forms of P in suspended matter were not affected by cyanobacterial blooms, indicating that the inorganic phosphorus is derived from the sediment after resuspension from the sediment due to wind and wave action. The contribution of the different P-fractions to TP in sediment and in suspended matter indicates that NH4Cl-P in the suspended matter is an important buffer for maintaining dissolved phosphorus in water.

New ways to break an old bond: the bacterial carbon-phosphorus hydrolases and their role in biogeochemical phosphorus cycling

Phosphonates are organophosphorus molecules that contain the highly stable C-P bond, rather than the more common, and more labile, C-O-P phosphate ester bond. They have ancient origins but their biosynthesis is widespread among more primitive organisms and their importance in the contemporary biosphere is increasingly recognized; for example phosphonate-P is believed to play a particularly significant role in the productivity of the oceans. The microbial degradation of phosphonates was originally thought to occur only under conditions of phosphate limitation, mediated exclusively by the poorly characterized C-P lyase multienzyme system, under Pho regulon control. However, more recent studies have demonstrated the Pho-independent mineralization by environmental bacteria of three of the most widely distributed biogenic phosphonates: 2-aminoethylphosphonic acid (ciliatine), phosphonoacetic acid, and 2-amino-3-phosphonopropionic acid (phosphonoalanine). The three phosphonohydrolases responsible have unique specificities and are members of separate enzyme superfamilies; their expression is regulated by distinct members of the LysR family of bacterial transcriptional regulators, for each of which the phosphonate substrate of the respective degradative operon serves as coinducer. Previously no organophosphorus compound was known to induce the enzymes required for its own degradation. Whole-genome and metagenome sequence analysis indicates that the genes encoding these newly described C-P hydrolases are distributed widely among prokaryotes. As they are able to function under conditions in which C-P lyases are inactive, the three enzymes may play a hitherto-unrecognized role in phosphonate breakdown in the environment and hence make a significant contribution to global biogeochemical P-cycling.

Stepwise construction of [Os6(CO)18(μ6-P)]-, a hexanuclear osmium cluster monoanion with trigonal-prismatic co-ordination for phosphorus: X-ray crystal structures of [Os6(μ-H)2(CO)20(MeCN)(μ3-PH)] and [PPh3Me][Os6(CO)18(μ6-P)]

Treatment of the labile cluster [Os3(CO)11(MeCN)] with PH3 affords the substituted product [Os3(CO)11(PH3)](1) in high yield. Subsequent reaction of (1) with Na2CO3 in MeOH, followed by acidification, gives the hydrido phosphido cluster [Os3(µ-H)(CO)10(µ-PH2)](2). When (2) is heated to 45–60 °C in the presence of [Os3(CO)11(MeCN)] a hexanuclear complex with the formulation [Os6(µ-H)2(CO)21(µ3-PH)](3) is obtained. If this reaction is repeated using [Os3(CO)10(MeCN)2] instead of [Os3(CO)11(MeCN)], an acetonitrile-containing product, [Os6(µ-H)2(CO)20(MeCN)(µ3-PH)](4), is obtained. An X-ray analysis of (4) shows that two Os3 triangular units are linked by a µ3-phosphinidene ligand, which symmetrically bridges an Os–Os edge of one triangle and is terminally co-ordinated to one Os atom of the second triangle. When (3) is treated with a weak base, such as [N(PPh3)2]Cl or [PPh3Me] Br, deprotonation to the corresponding cluster monoanion [Os6(µ-H)(CO)21(µ3-PH)]–(5) occurs. Treatment of (5) with a weak acid regenerates (3) in quantitative yield. Thermolysis of (3) leads to a closing up of the metal framework, affording the cluster [Os6(µ-H)(CO)18(µ6-P)], which readily deprotonates to give the anion [Os6(CO)18(µ6-P)]–(7) in the presence of [N(PPh3)2] Cl or [PPh3Me]Br. The same anion (7) may also be obtained by direct thermolysis of (5). An X-ray analysis of the [PPh3Me]+ salt of (7) confirms that the phosphorus occupies an interstitial site in a trigonal-prismatic hexaosmium framework, and co-ordinates to all six metal atoms with an average Os–P distance of 2.31 (1)Å. Proton and 31P n.m.r. data on all the new clusters are presented, and the position of the phosphorus resonance in the 31P n.m.r. spectrum is related to the changes in the environment of the phosphorus atom.

Elevated atmospheric CO2 changes phosphorus fractions in soils under a short rotation poplar plantation (EuroFACE)

Future high levels of atmospheric carbon dioxide (CO2) may increase biomass production of terrestrial plants and hence plant requirements for soil mineral nutrients to sustain a greater biomass production. Phosphorus (P), an element essential for plant growth, is found in soils both in inorganic and in organic forms. In this work, three genotypes of Populus were grown under ambient and elevated atmospheric CO2 concentrations (FACE) for 5 years. An N fertilisation treatment was added in years 4 and 5 after planting. Using a fractionation scheme, total P was sequentially extracted using H2O, NaOH, HCl and HNO3, and P determined as both molybdate (Mo) reactive and total P. Molybdate-reactive P is defined as mainly inorganic but also some labile organic P which is determined by Vanado-molybdophosphoric acid colorimetric methods. Organic P was also measured to assess all plant available and weatherable P pools. We tested the hypotheses that higher P demand due to increased growth is met by a depletion of easily weatherable soil P pools, and that increased biomass inputs increases the amount of organic P in the soil. The concentration of organic P increased under FACE, but was associated with a decrease in total soil organic matter. The greatest increase in the soil P due to elevated CO2 was found in the HCl-extractable P fraction in the non-fertilised treatment. In the NaOH-extractable fraction the Mo-reactive P increased under FACE, but total P did not differ between ambient and FACE. The increase in both the NaOH- and HCl-extractable fractions was smaller after N addition. The results showed that elevated atmospheric CO2 has a positive effect on soil P availability rather than leading to depletion.We suggest that the increase in the NaOH- and HCl-extractable fractions is biologically driven by organic matter mineralization, weathering and mycorrhizal hyphal turnover.