Abstract: This paper seeks a perspective on the forms of phosphorus which promote aquatic eutrophication, with the particular quest of establishing their sources. A short background traces the development of understanding of nutrient enrichment and the suppositions about the relative contributions of agriculture, sewage and detergent residues. Most aquatic systems, and their primary producers, are naturally deficient in biologically-available phosphorus. Aquatic plants have evolved very efficient phosphorus uptake mechanisms. The biomass responses to an increase in the supply of phosphorus are stoichiometrically predictable. The most bioavailable forms of phosphorus are in solution, as orthophosphate ions, or are readily soluble or elutable from loose combinations. Ready bioavailability coincides well with what is measurable as molybdate-reactive (MRP) or soluble-reactive phosphorus (SRP). Most other forms, including phosphates of the alkaline earth metals, aluminium and iron are scarcely available at all. Orthophosphate ions sorbed to metal oxides and hydroxides are normally not biologically available either, except through weak dissociation ('desorption'). The production of alkaline phosphatase provides organisms with an additional mechanism for accelerating the sequestration of phosphate from organic compounds. Bioavailable phosphate is liberated when redox- or alkali-sensitive metal hydroxides dissolve but these processes are minor contributors to the biological responses to nutrient enrichment. Most of the familiar eutrophication is attributable to the widespread application of secondary sewage treatment methods to the wastes emanating from a burgeoning and increasingly urbanised human population. The use of polyphosphate-based detergents, now in decline, has contributed to the problem. In aquatic systems, the additional phosphorus raises the biological supportive capacity, sometimes to the capacity of the next limiting factor (carbon, light, hydraulic retention or of another nutrient). At high orthophosphate loadings, the straight stoichiometric yield relationship between biomass yield and phosphorus a vailability is lost. Movements of phosphorus and its recycling within aquatic systems do not prevent the slow gravitation of phosphorus to the bottom substrata. The phosphorus retentivity of sediments depends upon their chemical composition. While oxide-hydroxide binding capacity in the surface sediments persists, they act as a sink for phosphorus and a control on further cycling. Iron-rich and clay-rich sediments perform best in these conditions; calcareous sediments least so. Eutrophication may lead to the exhaustion of sediment P-binding capacity. Non-sorbed phosphate is readily recyclable if primary producers have access to it. Recycling is most rapid in shallow waters (where sediment disturbance, by flow, by wind action and through bioturbation, is frequent and least in deep ventilated sediments. The contributions of phosphorus from catchments are assessed. The slow rate of weathering of (mostly apatitic) minerals, the role of chemical binding in soils and the incorporation and retentivity bv forested terrestrial ecosystems each contribute to the minimisation of phosphorus leakage to drainage waters. Palaeolimnological and experimental evidence confirms that clearance of land and ploughing its surface weakens the phosphorus retentivity of catchments. The phosphorus transferred from arable land to drainage remains dominated by sorbed fractions which are scarcely bioavailable. Some forms of intensive market gardening or concentrated stock rearing may mobilise phosphates to drainage but it is deduced that drainage from agricultural land is not commonly a major source of readily bioavailable phosphorus in water. Careful budgeting of the phosphates in run-off from over-fertilised soils may nevertheless show that a proportionately small loss of bioavailable phosphorus can still be highly significant in promoting aquatic plant production. The bioavailable-phosphorus (BAP) load achieving the OECD threshold of lake eutrophy (35 mg P m(-3)) is calculated to be equivalent to a terrestrial loss rate of approximately 17.5 kg BAP km(-2) year(-1)), or only 1-2% of a typical fertiliser application. The output is shown to be comparable with the P yield from secondary treatment of the sewage produced by a resident population of 30-44 persons km(-2). With tertiary treatment, the equivalence is with approximately 200 persons km(-2).

Abstract: The purpose of this study was to formulate topically effective controlled release ophthalmic acetazolamide liposomal formulations. Reverse-phase evaporation and lipid film hydration methods were used for the preparation of reversephase evaporation (REVs) and multilamellar (MLVs) acetazolamide liposomes consisting of egg phosphatidylcholine (PC) and cholesterol (CH) in the molar ratios of (7∶2), (7∶4), (7∶6), and (7∶7) with or without stearylamine (SA) or dicetyl phosphate (DP) as positive and negative charge inducers, respectively. The prepared liposomes were evaluated for their entrapment efficiency and in vitro release. Multilamellar liposomes entrapped greater amounts of drug than REVs liposomes. Drug loading was increased by increasing CH content as well as by inclusion of SA. Drug release rate showed an order of negatively charged > neutral > positively charged liposomes, which is the reverse of the data of drug loading efficiency. Physical stability study indicated that approximately 89%, 77%, and 69% of acetazolamide was retained in positive, negative, and neutral MLVs liposomal formulations up to a period of 3 months at 4°C. The intraocular pressure (IOP)-lowering activity of selected acetazolamide liposomal formulations was determined and compared with that of plain liposomes and acetazolamide solution. Multilamellar acetazolamide liposomes revealed more prolonged effect than REVs liposomes. The positively charged and neutral liposomes exhibited greater lowering in IOP and a more prolonged effect than the negatively charged ones. The positive multilamellar liposomes composed of PC:CH:SA (7:4:1) molar ratio showed the maximal response, which reached a value of −7.8±1.04 mmHg after 3 hours of topical administration.

Abstract: We report a new fluorescent chemosensor that displays an excellent selectivity for pyrophosphate over adenosine triphosphate or phosphate in 100% aqueous solution. A unique fluorescent change was observed upon formation of a 2+2 excimer of the chemosensor.

Abstract: Long-term changes in soil phosphorus influence ecosystem development and lead to a decline in the productivity of forests in undisturbed landscapes. Much of the soil phosphorus occurs in a series of organic compounds that differ in their availability to organisms, but changes in the relative abundance of these compounds during pedogenesis remain unknown. We used alkaline extraction and solution phosphorus-31 nuclear magnetic resonance spectroscopy to assess the chemical nature of soil organic phosphorus along a 120,000-year post-glacial chronosequence at Franz Josef, New Zealand. Inositol phosphates, DNA, phospholipids, and phosphonates accumulated rapidly during the first 500 years of soil development characterized by nitrogen limitation of biological productivity, but then declined slowly to low concentrations in older soils characterized by intense phosphorus limitation. However, the relative contribution of the various compounds to the total organic phosphorus varied along the sequence in dramatic and surprising ways. The proportion of inositol hexakisphosphate, conventionally considered to be relatively recalcitrant in the environment, declined markedly in older soils, apparently due to a corresponding decline in amorphous metal oxides, which weather to crystalline forms during pedogenesis. In contrast, the proportion of DNA, considered relatively bioavailable in soil, increased continually throughout the sequence, due apparently to incorporation within organic structures that provide protection from biological attack. The changes in soil organic phosphorus coincided with marked shifts in plant and microbial communities, suggesting that differences in the forms and bioavailability of soil organic phosphorus have ecological significance. Overall, the results strengthen our understanding of phosphorus transformations during pedogenesis and provide important insight into factors regulating the composition of soil organic phosphorus.

Abstract: Bioceramic bone substitutes with programmed architecture were manufactured at room temperature in this study using a novel 3D printing process that combined 3D powder printing with calcium phosphate cement chemistry. During printing, biphasic α/β-tricalcium phosphate (Ca3(PO4)2, TCP) powder reacted with a liquid component consisting of phosphoric acid solution to form a matrix of dicalcium phosphate dihydrate (CaHPO4·H2O, DCPD, brushite) and unreacted TCP. Printed samples showed compressive strengths between 0.9–8.7 MPa after printing depending on the acid concentration. A further strength improvement to a maximum of 22 MPa could be obtained by additional hardening of the samples in phosphoric acid for three one minute washes. After this treatment, the samples mainly consisted of brushite with minor phases of unreacted TCP and a lesser amount of dicalcium phosphate anhydrate (CaHPO4, DCPA, monetite). Hydrothermal conversion of brushite to DCPA resulted in an increase of porosity of approximately 13 % and a decrease of strength to 15 MPa, however the resorption rate in vivo was increased as demonstrated after intramuscular implantation over 56 weeks. Major advantages compared with commonly used sintering techniques are the low processing temperature, which enables the fabrication of thermally instable and degradable matrices of secondary calcium phosphates.

Abstract: We used fluorescence microscopy to determine how polymerization of Mg-ADP-actin depends on the concentration of phosphate. From the dependence of the elongation rate on the actin concentration and direct observations of depolymerizing filaments, we measured the polymerization rate constants of ADP-actin and ADP-Pi-actin. Saturating phosphate reduces the critical concentration for polymerization of Mg-ADP-actin from 1.8 to 0.06 μM almost entirely by reducing the dissociation rate constants at both ends. Saturating phosphate increases the barbed end association rate constant of Mg-ADP-actin 15%, but this value is still threefold less than that of ATP-actin. Thus, ATP hydrolysis without phosphate dissociation must change the conformation of polymerized actin. Analysis of depolymerization experiments in the presence of phosphate suggests that phosphate dissociation near the terminal subunits is much faster than in the interior. Remarkably, 10 times more phosphate is required to slow the depolymerization of the pointed end than the barbed end, suggesting a weak affinity of phosphate near the pointed end. Our observations of single actin filaments provide clues about the origins of the difference in the critical concentration at the two ends of actin filaments in the presence of ATP.

Abstract: The casein phosphopeptides (CPP) are derived from the milk protein casein by tryptic digestion. The CPP, containing the sequence -Pse-Pse-Pse-Glu-Glu- where Pse is a phosphoseryl residue, stabilize calcium and phosphate ions in aqueous solution and make these essential nutrients bioavailable. Under alkaline conditions the calcium phosphate is present as an alkaline amorphous phase complexed by the CPP, referred to as casein phosphopeptide-amorphous calcium phosphate (CPP-ACP). The CPP-ACP complexes readily incorporate fluoride ions forming casein phosphopeptide-amorphous calcium fluoride phosphate (CPP-ACFP). A mechanism is discussed which provides a rationale for the ability of the CPP-ACP to remineralize carious lesions in dental enamel. Clinical applications of the CPP-ACP as agents in the treatment of dental caries and other hypomineralized conditions are reviewed. It is concluded that the CPP are a safe and novel carrier for calcium, phosphate and hydroxide (fluoride) ions to promote enamel remineralization with application in oral care products, dental professional products and foodstuffs.

Abstract: The design and fabrication of scaffolds and biodegradable devices using slow-degrading polymers and composites (degradation/resorption > 2 years) involve the necessity for long-term in vitro and in vivo studies. If multiple designs and materials need to be tested, then this would use much time and financial resources. Accelerated degradation systems aim to achieve comparable degradation profiles within a shorter period of time. This investigation considers the hydrolytic degradation of polycaprolactone (PCL) and PCL–calcium phosphate (CaP) scaffolds in 5 mol L−1 NaOH at 37 °C. The scaffolds degrade via surface erosion, which proceeds in a consistent and predictable manner. The hydrolytic degradation of PCL-based scaffolds alone is slow, governed by their high molecular weights, crystallinity, hydrophobicity, surface-to-volume ratio and porosity. The incorporation of CaP significantly increases the degradation rate. Copyright © 2007 Society of Chemical Industry

Abstract: During the Archean, massive amounts of iron were deposited in the form of banded iron formations. It has been suggested that sedimenting particles of ferric oxyhydroxide may have stripped dissolved phosphate from the oceans, causing a reduction in phytoplankton productivity. However, that model does not take into account the high concentration of dissolved silica that was present in seawater at that time. We show experimentally that silica effectively competes with phosphate for sorption sites on ferrihydrite particles. Furthermore, coprecipitation of silica with ferrihydrite reduces particle reactivity toward phosphate. Hence, Archean oceans probably contained considerably more phosphate than previously predicted.

Abstract: Phosphate removal from an aquatic environment was investigated using La(III)-, Ce(III)- and Fe(III)-loaded orange waste. The adsorption isotherm, the kinetics of adsorption and the effect of pH on the removal of phosphate have been examined. The % removal of phosphate using La(III)- and Ce(III)-loaded orange waste gel increases with increasing pH within the range of 5–7 but decreases when the pH is increased beyond this range. The equilibrium sorption was observed to be in accordance with Langmuir type adsorption and the maximum adsorption capacity was evaluated as 13.94 mg P/g of dry gel for all the three types of gels. Kinetic studies revealed that 15 h is enough to reach equilibrium in batch experiments. Fixed bed sorption experiments confirmed the continuous phosphate adsorption and elution capability of such simply modified gels. Due to their low cost, availability and significantly high adsorption capability, metal-loaded SOW gels can be effectively employed for the removal of phosphate from water.

Abstract: Phosphate anions, both inorganic and organic, hold a unique position in nature, as they take part in almost all metabolic processes. Nucleotide phosphates such as AMP or ATP are important for their role in bioenergetics, metabolism, and transfer of genetic information. Phosphates in biological liquids are often present in high concentrations and may be utilized in the diagnosis of certain diseases. Human serum contains 0.80– 1.45 mm phosphate; higher phosphate levels are directly connected to cardiovascular disease and acute renal failure. Similarly, ATP is present in resting muscle at a concentration of 4 mm, and in erythrocytes at a concentration of just under 2 mm. Numerous materials have been developed to sense phosphate ions in water at biological pH values. The sensors based on anion-induced enhancement of intrinsic fluorescence (turn-on) are attractive as they offer the potential for high sensitivity 7] and, unlike the displacement assays, are instantly reversible. Alas, few fluorescence-turn-on sensors exist for phosphate that function in electrolyte solutions. To the best of our knowledge, fluorescence-turn-on sensors capable of sensing phosphate ions in complex biological milieu, such as blood serum, have not yet been developed. Recently, we demonstrated that simple anion sensors based on hydrogen-bonding interactions can bind and sense anions in hydrophilic polymer matrices, despite their inability to bind anions in water. 11] This method combined with the sensitivity of the fluorescence-turn-on signaling could allow for the sensing of phosphate ions in aqueous environments, including biological milieu such as blood serum. Here, we present tripodal sensor molecules S1–S8 (Scheme 1) based on 1,3,5-triaminomethyl-2,4,6-triethylbenzene which can form arrays of six hydrogen-bond donors.

Abstract: Uranium contamination is an environmental concern at the Department of Energy's Field Research Center in Oak Ridge, Tennessee. In this study, we investigated whether phosphate biomineralization, or the aerobic precipitation of U(VI)-phosphate phases facilitated by the enzymatic activities of microorganisms, offers an alternative to the more extensively studied anaerobic U(VI) bioreduction. Three heterotrophic bacteria isolated from FRC soils were studied for their ability to grow and liberate phosphate in the presence of U(VI) and an organophosphate between pH 4.5 and 7.0. The objectives were to determine whether the strains hydrolyzed sufficient phosphate to precipitate uranium, to determine whether low pH might have an effect on U(VI) precipitation, and to identify the uranium solid phase formed during biomineralization. Two bacterial strains hydrolyzed sufficient organophosphate to precipitate 7395% total uranium after 120 h of incubation in simulated groundwater. The highest rates of uranium precipitation and phosphatase activity were observed between pH 5.0 and 7.0. EXAFS spectra identified the uranyl phosphate precipitate as an autunite/meta-autunite group mineral. The results of this study indicate that aerobic heterotrophic bacteria within a uranium-contaminated environment that can hydrolyze organophosphate, especially in low pH conditions, may play an important role in the bioremediation of uranium.

Abstract: Phosphate ions are responsible for the algal bloom in receiving water bodies and aesthetic problems in drinking water. From the environmental and economic points of view, management of such a contaminant and valuable resource is very important. The present paper deals with the removal of inorganic phosphate ions from aqueous solutions using synthetic HSZ 330 HUD Zeolite (Si/Al ratio: 2.75−3.25) and its Al3+-activated form (Al-HUD) as adsorbents. Equilibrium and kinetic experiments were performed to study the effects of operating conditions such as adsorbent mass, solution pH, coexisting ions, and initial concentration on either the capacity or the rate of phosphate uptake by the zeolites. As a result, it was found that the efficiency of phosphate removal by the zeolites increased with an increase in adsorbent mass and a decrease in solution pH. Outer-sphere complex-forming ions such as nitrate, sulfate, and chloride improved slightly the phosphate removal efficiency while fluoride ions, which form inner-...

Abstract: The kinetics and the equilibrium adsorption of phosphate by collodion-coated alumina granules were investigated. Collodion-coated alumina can serve as a sorbent for phosphates in the treatment of hyperphosphatemic patients by haemoperfusion. The collodion coating lowers the surface area available for adsorption. The kinetics of adsorption were investigated by experiments in which the initial phosphate concentration, the quantity of sorbent and the grain size of sorbent were varied. The rate of adsorption is proportional to tα-1 where t is time and α is around 0.7.

Abstract: The mechanisms by which phosphorus homeostasis is preserved in mammals are not completely understood. We demonstrate the presence of a mechanism by which the intestine detects the presence of increased dietary phosphate and rapidly increases renal phosphate excretion. The mechanism is of physiological relevance because it maintains plasma phosphate concentrations in the normal range after ingestion of a phosphate-containing meal. When inorganic phosphate is infused into the duodenum, there is a rapid increase in the renal fractional excretion of phosphate (FE Pi). The phosphaturic effect of intestinal phosphate is specific for phosphate because administration of sodium chloride does not elicit a similar response. Phosphaturia after intestinal phosphate administration occurs in thyro-parathyroidectomized rats, demonstrating that parathyroid hormone is not essential for this effect. The increase in renal FE Pi in response to the intestinal administration of phosphate occurs without changes in plasma concentrations of phosphate (filtered load), parathyroid hormone, FGF-23, or secreted frizzled related protein-4. Denervation of the kidney does not attenuate phosphaturia elicited after intestinal phosphate administration. Phosphaturia is not elicited when phosphate is instilled in other parts of the gastrointestinal tract such as the stomach. Infusion of homogenates of the duodenal mucosa increases FE Pi, which demonstrates the presence of one or more substances within the intestinal mucosa that directly modulate renal phosphate reabsorption. Our experiments demonstrate the presence of a previously unrecognized phosphate gut-renal axis that rapidly modulates renal phosphate excretion after the intestinal administration of phosphate.

Abstract: Phoshpate-modified titania (P−TiO2) samples of varying phosphate contents were prepared by the sol−gel method, and the photocatalytic activity was tested in the gas-phase degradation of ethanol at room temperature. DRIFT, UV−vis−DR, N2 adsorption, and XRD methods were used to characterize the structural properties of the P−TiO2 samples. XPS, ICP-AES, and SAXS investigations were additionally performed to further clarify the structural changes of the TiO2 sample due to phosphate modification. We showed that the phosphate ions reacted with the TiO2 surface and that a new crystalline titanium phosphate phase appeared during the calcination process. It was found that the structural and optical properties of the titania samples are strongly influenced by their phosphate content. The photocatalytic activity of the P−TiO2 was compared with that of Degussa P25 titanium dioxide by ethanol photooxidation in the gas phase. We have shown that total degradation of ethanol is significantly faster on P−TiO2 samples with...

Abstract: Red mud is the waste of alumina industry and has high TiO2 and Fe2O3 content which are active components for the adsorption of anion pollutants. In this study, the uptake of phosphate by red mud activated by heat treatment and acid-heat treatment was investigated. The factors influencing the adsorption were also investigated. The result showed that the red mud sample treated using acid-heat method at 80 degrees C with 0.25 mol/L HCl for 2 h achieved the highest phosphate removal. For the heat-activated red mud, the sample heated at 700 degrees C for 2 h preformed better than the other heat treatment. Phosphate removal by the activated red mud was significantly pH dependent, and pH 7 was the optimal pH for phosphate removal. The adsorption fits Langmuir isotherm model well and the maximum adsorption capacities of the acid-heat activated red mud and the heat activated samples were 202.9 mgP/g and 155.2 mgP/g, respectively.

Abstract: Phosphate rock contains up to 1% lanthanide (rare earths) oxides present in isomorphous substitution for Ca2+. Lanthanum, cerium and neodymium form about 80% of the total. When the rock is leached with H2SO4 the lanthanides are mostly (about 70%) lost in the gypsum residue. When the rock is leached with HNO3 or HC1, more than 80% can be recovered without interference with fertiliser production. At an annual production of 130 million tons, phosphate rock represents an important source of lanthanides. The different methods of recovery are reviewed.