SciCombinator

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Concept: Phosphorus

189

We provide evidence that citrate anions bridge between mineral platelets in bone and hypothesize that their presence acts to maintain separate platelets with disordered regions between them rather than gradual transformations into larger, more ordered blocks of mineral. To assess this hypothesis, we take as a model for a citrate bridging between layers of calcium phosphate mineral a double salt octacalcium phosphate citrate (OCP-citrate). We use a combination of multinuclear solid-state NMR spectroscopy, powder X-ray diffraction, and first principles electronic structure calculations to propose a quantitative structure for this material, in which citrate anions reside in a hydrated layer, bridging between apatitic layers. To assess the relevance of such a structure in native bone mineral, we present for the first time, to our knowledge, (17)O NMR data on bone and compare them with (17)O NMR data for OCP-citrate and other calcium phosphate minerals relevant to bone. The proposed structural model that we deduce from this work for bone mineral is a layered structure with thin apatitic platelets sandwiched between OCP-citrate-like hydrated layers. Such a structure can explain a number of known structural features of bone mineral: the thin, plate-like morphology of mature bone mineral crystals, the presence of significant quantities of strongly bound water molecules, and the relatively high concentration of hydrogen phosphate as well as the maintenance of a disordered region between mineral platelets.

Concepts: DNA, Scientific method, Bone, Apatite, Water, Phosphate, Phosphorus, Salt

136

The ability to solubilize fixed inorganic phosphorus (P) for plant growth is important for increasing crop yield. More P can be released by inoculating soil with inorganic-phosphate-solubilizing bacteria (iPSBs). We used 96-well microplates instead of traditional 200-mm petri dishes to rapidly screen iPSB strains for their solubilizing ability. We simultaneously obtained 76 iPSB isolates from 576 wells containing two agricultural soils. This method conveniently identified positive iPSB strains and effectively prevented fungal cross-contamination. Maximum-likelihood phylogenetic trees of the isolated strains showed that Bacillus megaterium was the most dominant iPSB, and strains Y99, Y95, Y924 and Y1412 were selected as representatives for the analysis of P solubilization. Succinic acid was the main organic acid of B. megaterium for releasing P. It was strongly correlated with the increase in soluble P concentration during 168 h of incubation of these four strains. pH was negatively exponentially correlated with the amount of soluble P in the medium, and the amount of succinic acid was strongly linearly correlated with the amount of P released (P < 0.001), suggesting that organic acid may mobilize microbial P. Our study provides an efficient and effective method for identifying and analyzing the growth of iPSB strains able to solubilize inorganic P and gives a better understanding of the mechanism of P solubilization.

Concepts: Oxygen, Bacteria, Agriculture, Acid, Soil, Bacillus, Phosphorus, Bacillus megaterium

101

In 2011, Lake Erie experienced the largest harmful algal bloom in its recorded history, with a peak intensity over three times greater than any previously observed bloom. Here we show that long-term trends in agricultural practices are consistent with increasing phosphorus loading to the western basin of the lake, and that these trends, coupled with meteorological conditions in spring 2011, produced record-breaking nutrient loads. An extended period of weak lake circulation then led to abnormally long residence times that incubated the bloom, and warm and quiescent conditions after bloom onset allowed algae to remain near the top of the water column and prevented flushing of nutrients from the system. We further find that all of these factors are consistent with expected future conditions. If a scientifically guided management plan to mitigate these impacts is not implemented, we can therefore expect this bloom to be a harbinger of future blooms in Lake Erie.

Concepts: Algae, Cyanobacteria, Time, Water, Eutrophication, Algal bloom, Phosphorus, Dinoflagellate

49

Increasing diffuse nitrate loading of surface waters and groundwater has emerged as a major problem in many agricultural areas of the world, resulting in contamination of drinking water resources in aquifers as well as eutrophication of freshwaters and coastal marine ecosystems. Although empirical correlations between application rates of N fertilizers to agricultural soils and nitrate contamination of adjacent hydrological systems have been demonstrated, the transit times of fertilizer N in the pedosphere-hydrosphere system are poorly understood. We investigated the fate of isotopically labeled nitrogen fertilizers in a three-decade-long in situ tracer experiment that quantified not only fertilizer N uptake by plants and retention in soils, but also determined to which extent and over which time periods fertilizer N stored in soil organic matter is rereleased for either uptake in crops or export into the hydrosphere. We found that 61-65% of the applied fertilizers N were taken up by plants, whereas 12-15% of the labeled fertilizer N were still residing in the soil organic matter more than a quarter century after tracer application. Between 8-12% of the applied fertilizer had leaked toward the hydrosphere during the 30-y observation period. We predict that additional exports of (15)N-labeled nitrate from the tracer application in 1982 toward the hydrosphere will continue for at least another five decades. Therefore, attempts to reduce agricultural nitrate contamination of aquatic systems must consider the long-term legacy of past applications of synthetic fertilizers in agricultural systems and the nitrogen retention capacity of agricultural soils.

Concepts: Agriculture, Water, Fertilizer, Eutrophication, Soil, Nitrogen, Phosphorus, Manure

32

High crop yields depend on the continuous input of orthophosphate (PO(4)(−3))-based fertilizers and herbicides. Two major challenges for agriculture are that phosphorus is a nonrenewable resource and that weeds have developed broad herbicide resistance. One strategy to overcome both problems is to engineer plants to outcompete weeds and microorganisms for limiting resources, thereby reducing the requirement for both fertilizers and herbicides. Plants and most microorganisms are unable to metabolize phosphite (PO(3)(−3)), so we developed a dual fertilization and weed control system by generating transgenic plants that can use phosphite as a sole phosphorus source. Under greenhouse conditions, these transgenic plants require 30–50% less phosphorus input when fertilized with phosphite to achieve similar productivity to that obtained by the same plants using orthophosphate fertilizer and, when in competition with weeds, accumulate 2–10 times greater biomass than when fertilized with orthophosphate.

Concepts: Photosynthesis, Ammonia, Fertilizer, Phosphate, Nitrogen, Phosphorus, Weed, Glyphosate

31

It has been hypothesized that before the emergence of modern DNA-RNA-protein life, biology evolved from an “RNA world.” However, synthesizing RNA and other organophosphates under plausible early Earth conditions has proved difficult, with the incorporation of phosphorus (P) causing a particular problem because phosphate, where most environmental P resides, is relatively insoluble and unreactive. Recently, it has been proposed that during the Hadean-Archean heavy bombardment by extraterrestrial impactors, meteorites would have provided reactive P in the form of the iron-nickel phosphide mineral schreibersite. This reacts in water, releasing soluble and reactive reduced P species, such as phosphite, that could then be readily incorporated into prebiotic molecules. Here, we report the occurrence of phosphite in early Archean marine carbonates at levels indicating that this was an abundant dissolved species in the ocean before 3.5 Ga. Additionally, we show that schreibersite readily reacts with an aqueous solution of glycerol to generate phosphite and the membrane biomolecule glycerol-phosphate under mild thermal conditions, with this synthesis using a mineral source of P. Phosphite derived from schreibersite was, hence, a plausible reagent in the prebiotic synthesis of phosphorylated biomolecules and was also present on the early Earth in quantities large enough to have affected the redox state of P in the ocean. Phosphorylated biomolecules like RNA may, thus, have first formed from the reaction of reduced P species with the prebiotic organic milieu on the early Earth.

Concepts: DNA, Molecular biology, Organism, Life, Chemistry, Phosphate, Solubility, Phosphorus

28

In the protist world, the ciliate Coleps hirtus (phylum Ciliophora, class Prostomatea) synthesizes a peculiar biomineralized test made of alveolar plates, structures located within alveolar vesicles at the cell cortex. Alveolar plates are arranged by overlapping like an armour and they are thought to protect and/or stiffen the cell. Although their morphology is species-specific and of complex architecture, so far almost nothing is known about their genesis, their structure and their elemental and mineral composition. We investigated the genesis of new alveolar plates after cell division and examined cells and isolated alveolar plates by electron microscopy, energy-dispersive X-ray spectroscopy, FTIR and X-ray diffraction. Our investigations revealed an organic mesh-like structure that guides the formation of new alveolar plates like a template and the role of vesicles transporting inorganic material. We further demonstrated that the inorganic part of the alveolar plates is composed out of amorphous calcium carbonate. For stabilization of the amorphous phase, the alveolar vesicles, the organic fraction and the element phosphorus may play a role.

Concepts: DNA, X-ray, Mineral, X-ray crystallography, Calcium carbonate, Phosphorus, Ciliate, Coleps

28

Waste streams offer a compelling opportunity to recover phosphorus (P). 15-20% of world demand for phosphate rock could theoretically be satisfied by recovering phosphorus from domestic waste streams alone. For very dilute streams (<10mgPL(-1)), including domestic wastewater, it is necessary to concentrate phosphorus in order to make recovery and reuse feasible. This review discusses enhanced biological phosphorus removal (EBPR) as a key technology to achieve this. EBPR relies on polyphosphate accumulating organisms (PAOs) to take up phosphorus from waste streams, so concentrating phosphorus in biomass. The P-rich biosolids can be either directly applied to land, or solubilized and phosphorus recovered as a mineral product. Direct application is effective, but the product is bulky and carries contaminant risks that need to be managed. Phosphorus release can be achieved using either thermochemical or biochemical methods, while recovery is generally by precipitation as struvite. We conclude that while EBPR technology is mature, the subsequent phosphorus release and recovery technologies need additional development.

Concepts: DNA, Biology, Organism, Water, Phosphate, Phosphorus, Enhanced biological phosphorus removal, Recovery

27

We report the synthesis and photolytic properties of caged inorganic phosphates (Pi compounds) based on the 2-(4'-{bis[2-(2-methoxyethoxy)ethyl]amino}-4-nitro-[1,1'-biphenyl]-3-yl)propan-1-ol (EANBP) and 7-(diethylamino)coumarin-4-yl]methyl (DEACM) protecting groups. The EANBP-Pi showed unprecedented photolysis efficiency at 405 nm, with 95 % release of free phosphate and a quantum yield of 0.28. Thanks to the high two-photon sensitivity of the EANBP chromophore, Pi release through two-photon photolysis is also possible, with an action cross section of 20.5 GM at 800 nm. Two bioactivatable acetoxymethyl protection groups were added to the “caged-Pi” compounds. The resulting triesters of phosphoric acid were able to diffuse through the cellular membranes of plant cells. Once inside a cell, the cleavage of these biocleavable motifs by intracellular esterases allows intracellular accumulation of EANBP-Pi. Bis(AM)-EANBP-Pi therefore represents a very attractive tool for study of the Pi signal transduction cascade in living cells.

Concepts: Protein, Organism, Cell membrane, Cell biology, Phosphate, Phosphoric acid, Phosphorus, Transfection

27

Potassium Dihydrogen Phosphate (KDP) doped with l-aspartic acid has been grown by solvent slow evaporation technique from a mixture of aqueous solution of KDP and 0.7% of l-aspartic acid at room temperature. The grown crystals were characterized by powder X-ray diffraction, UV-visible, FTIR analysis. The doping of aspartic acid was confirmed by FTIR spectrum. The Nonlinear optical property (SHG) of l-aspartic acid doped KDP has been confirmed. Microhardness studies were carried out on the grown crystal.

Concepts: Amino acid, Diffraction, Fundamental physics concepts, Chemistry, Solubility, Solutions, Phosphorus, Aspartic acid