Polyphosphate Formation Research Articles

Studies on the pyrolysis and potential flame retardancy of low-substituted starch phosphates

Investigations on the pyrolysis and potential flame retardancy imparted by solvent-free and semi-dry phosphorylation of different starches using sodium orthophosphates were conducted. The samples – low-substituted starch phosphates (SP) with degrees of substitution DSP < 0.5 - were subjected to differential scanning calorimetry, thermogravimetry coupled with evolved gas analysis and pyrolysis – gas chromatography – mass spectrometry. The data obtained as well as features of charring residues examined using microscopic and spectroscopic methods were related to structural aspects of SP – analysed by means of various spectroscopic techniques - and compared with those of native starches. It was found that charring and polyphosphate formation and the thermal resistance of the solid SP residues increased significantly if the DSP was at least 0.1. Accordingly, the exothermal decomposition, the temperature-induced loss of mass and the decomposition rates of SP decreased distinctly compared to native starch. The activation temperatures of SP and the formation of low-molecular pyrolysis products including aliphatic, cyclic, and aromatic aldehydes and ketones as well as anhydrosugars decreased markedly, even at DSP < 0.1. The results confirm the potential flame-retardancy of SP achieved by flame-inhibiting effects, despite low phosphorylation degrees, in both the gas and condensed phases.

The impact of apatite on sulfuric acid baking of a monazite concentrate and the benefit of goethite addition on rare earth leaching

Sulfuric acid baking of monazite ((Ce,La,Th)PO4) bearing ores is one of the major processes used in commercial production of rare earth elements. In hydrothermal vein type rare earth deposits, apatite is often found together with monazite. Rare earth enriched fluorapatite ores may also contain significant amounts of rare earths hosted in monazite. An understanding of the effect of apatite on the sulfuric acid baking of monazite is therefore important for the development of effective sulfuric acid based treatment methods for such ores. In this work, the addition of a natural hydroxyapatite (Ca5(PO4)3(OH)) sample to a monazite acid bake followed by acid leach was investigated using a combination of chemical analyses, SEM-EDS, XRD and TG-DSC. Hydroxyapatite addition significantly decreased the dissolution of rare earth elements from monazite in the leach after baking at temperatures above 300 °C. For a bake temperature of 500 °C, the rare earth dissolution in the leach dropped from 80% for monazite alone, to 30% for a 1:1 (w/w) addition of hydroxyapatite. This decrease in rare earth leaching was attributed to the formation of an insoluble thorium and rare earth bearing polyphosphate. The rare earth elements were incorporated into this polyphosphate phase in preference to calcium. At 800 °C, monazite was re-formed, causing a further reduction in rare earth extraction, while simultaneous formation of calcium pyrophosphate (Ca2P2O7) led to an increase in calcium and phosphorus dissolution. The detrimental effect of apatite could be partially overcome by the addition of goethite. Addition of goethite to the acid bake of a monazite/apatite mixture at 500 °C improved the total rare earth dissolution from 29% to 85% in the subsequent leach. Results also demonstrated that the order of reactivity, in terms of formation of polyphosphates is Fe > REE > Ca.

Co-inoculation of phosphate-solubilizing bacteria and phosphate accumulating bacteria in phosphorus-enriched composting regulates phosphorus transformation by facilitating polyphosphate formation

This study aimed to explore the impact of co-inoculating phosphate-solubilizing bacteria (PSB) and phosphate accumulating bacteria (PAB) on phosphorus forms transformation, microbial biomass phosphorus (MBP) and polyphosphate (Poly-P) accumulation, bacterial community composition in composting, using high throughput sequencing, PICRUSt 2, network analysis, structural equation model (SEM) and random forest (RF) analysis. The results demonstrated PSB-PAB co-inoculation (T1) reduced Olsen-P content (1.4 g) but had higher levels of MBP (74.2 mg/kg) and Poly-P (419 A.U.) compared to PSB-only (T0). The mantel test revealed a significantly positive correlation between bacterial diversity and both bioavailable P and MBP. Halocella was identified as a key genus related to Poly-P synthesis by network analysis. SEM and RF analysis showed that pH and bacterial community had the most influence on Poly-P synthesis, and PICRUSt 2 analysis revealed inoculation of PAB increased ppk gene abundance in T1. Thus, PSB-PAB co-inoculation provides a new idea for phosphorus management.

Phosphorus promotion on hydrothermal stability of ZSM-5 by P precursors with different molecular sizes

The promotional effects of phosphorous modification on ZSM-5 zeolites by phosphorus oxyacids (H4P2O7, H3PO4, H3PO3, and H3PO2) with different molecular sizes were investigated with catalytic cracking of n-tetradecane as the probe reaction. It was verified that the diffusion of P precursor molecules into ZSM-5 channels was important to prevent aggregation of P species for better stabilization on tetra-coordinated framework aluminum. Meanwhile, the P–Al interaction was proposed based on results of 27Al, 31P, and 29Si MAS NMR. With H3PO2 as the P precursor, easy diffusion into ZSM-5 channels contributed to less formation of polyphosphates, homogeneous distribution of P species, better reserved crystallinity, microporous area and acidic sites for improving cracking performance of n-tetradecane.

A Wild Pseudomonas has appeared: An Exercise in Bacterial Isolation and Identification

<span id="docs-internal-guid-8e962b78-7fff-c5ee-bc79-1ba2a6c149e3"><span>The aim of our research was to isolate and identify wild type </span><span>Pseudomonas putida </span><span>from soil in various cities of San Gabriel Valley. </span><span>P. putida </span><span>is</span><span>capable of biomineralization. Biomineralization can potentially be used as a method of phosphorus recovery by using bacteria to produce phosphate rich struvite. In isolating bacteria for further observation, fluorescence was used as a primary determinant in identifying possible </span><span>Pseudomonas </span><span>strains as fluorescence is a common trait shared among varying </span><span>Pseudomonas </span><span>species; </span><span>P. putida, P. aeruginosa</span><span>,</span><span> P. fluorescens</span><span>,</span><span> P. cichorii</span><span>,</span><span> P. chlororaphis</span><span>,</span><span> P. syringae</span><span>,</span><span>and </span><span>P. aureofaciens</span><span>. King’s B agar was used to promote the production of pyoverdine in these strains (allowing for direct identification based on a green fluorescence under UV light) as this medium has specific ingredients that enhance pigment production.</span><span>These fluorescent bacteria were then further isolated from each other and identified using biochemical methods including catalase, oxidase, nitrate reduction, and gelatin hydrolysis tests to differentiate </span><span>P. putida </span><span>from the six other fluorescent </span><span>Pseudomonas </span><span>species. Of the 21 total samples isolated based on fluorescence, 5 of the samples were determined to be potential </span><span>P. putida. </span><span>While the biochemical assays were conducted, the isolated samples were placed in refrigeration for 3 weeks. After the biochemical tests were completed and 3 weeks had passed, visible crystals had formed in the potential </span><span>P. putida</span><span>. Albert’s metachromatic staining was performed to determine the presence of polyphosphate granules. Ultimately, each potential </span><span>P. putida</span><span> that produced crystals also showed polyphosphate granules when Albert’s stained, which further connects crystal formation with prior polyphosphate formation.</span></span>

Slow release fertilizers based on polyphosphate/montmorillonite nanocomposites for improving crop yield

Nanocomposites are promising materials for the development of novel and environmentally friendly fertilizers that can delay the release of nutrients. In this study, a novel high-strength spherical nanocomposite fertilizer was prepared via agglomeration and granulation using montmorillonite, urea phosphate, urea, and potassium chloride as raw materials. The properties and morphology of the prepared fertilizer were characterized by Fourier Transform Tnfrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), Thermogravimetric Analysis (TGA) and X-ray Computed Tomography (XCT) techniques. FT-IR analysis identified the formation of polyphosphate in fertilizer and hydrogen bonds between polyphosphate and montmorillonite. XRD analysis showed increased montmorillonite interlayer spacing and confirmed the formation of polyphosphate-montmorillonite nanocomposites. The effects of raw material mass ratio, reaction time, and reaction temperature on the strength and fluidity of nanocomposite fertilizer granules and the optimum preparation process was obtained by the response surface method (RSM-CCD). The optimum preparation process was obtained as follows: reaction temperature, 103 °C; reaction time, 237 min; and mass ratio, 1:1:0.93:1 (urea phosphate: urea: potassium chloride: montmorillonite). Under these optimum conditions, the particle hardness and angle of repose of the prepared fertilizer were 64.75 ± 0.48 N and 30.84 ± 0.95°. Nutrient release and agronomic effectiveness of the fertilizer was evaluated using column leaching and pot experiments, respectively. The column leaching experiment and XCT analysis demonstrated that the nanocomposite structure was responsible for the slow nutrient release. The pot experiment showed that compared with the traditional fertilizer, the soil nitrate and available phosphorus was increased by 28.02% and 43.45%, respectively, and the maize yield was increased by 24.27% with the application of prepared fertilizer. This work provides support for the preparation of high-strength spherical nanocomposite fertilizers and their large-scale applications in modern mechanical agriculture.

Genome-wide screen in human plasma identifies multifaceted complement evasion of Pseudomonas aeruginosa

Pseudomonas aeruginosa, an opportunistic Gram-negative pathogen, is a leading cause of bacteremia with a high mortality rate. We recently reported that P. aeruginosa forms a persister-like sub-population of evaders in human plasma. Here, using a gain-of-function transposon sequencing (Tn-seq) screen in plasma, we identified and validated previously unknown factors affecting bacterial persistence in plasma. Among them, we identified a small periplasmic protein, named SrgA, whose expression leads to up to a 100-fold increase in resistance to killing. Additionally, mutants in pur and bio genes displayed higher tolerance and persistence, respectively. Analysis of several steps of the complement cascade and exposure to an outer-membrane-impermeable drug, nisin, suggested that the mutants impede membrane attack complex (MAC) activity per se. Electron microscopy combined with energy-dispersive X-ray spectroscopy (EDX) revealed the formation of polyphosphate (polyP) granules upon incubation in plasma of different size in purD and wild-type strains, implying the bacterial response to a stress signal. Indeed, inactivation of ppk genes encoding polyP-generating enzymes lead to significant elimination of persisting bacteria from plasma. Through this study, we shed light on a complex P. aeruginosa response to the plasma conditions and discovered the multifactorial origin of bacterial resilience to MAC-induced killing.

Phosphate-solubilizing microorganisms regulate the release and transformation of phosphorus in biochar-based slow-release fertilizer

Coupling phosphate-solubilizing microorganisms (PSM) can improve the availability of phosphorous (P) in biochar-based slow-release P fertilizers (BPF). However, the mechanism in release and transformation of P in BPF regulated by PSM is still unclear. Herein, the biocompatibility and the adhesion behaviors of BPF and PSM (Enterobacter hormaechei Rs-198) in soil were firstly studied, and a 90 days' laboratory-scale soil incubation experiment of BPF and Rs-198 was performed to study the transformation of P of BPF. The results show that BPF has a good biocompatibility for Rs-198 due to its low aromaticity, graphitization and free radicals' content (0.084 mg/g). Rs-198 are adhered to the surface of BPF in soil due to the high negative secondary energy minimum and low total interaction energy between Rs-198 and BPF. Available P in the incubation of BPF and Rs-198 (BR treatment) is significantly higher than that of the incubation of BPF (BF treatment) at initial 60 days. However, the content of available P in BR treatment is much lower compared with that in BF treatment on day 90, which is attributed to the entrapment of released P from BPF by Rs-198 and the formation of polyphosphate (polyP) rather than bound with soil mineral. Overall, this study presents new insights into the transformation of P in BPF regulated by PSM.

Influence of Additives Concentration on the Electrical Properties and the Tribological Behaviour of Three Automatic Transmission Fluids

Placing an electric motor (EM) inside the transmission housing of a hybrid electric vehicle (HEV) implies that the automatic transmission fluid (ATF) needs to accomplish additional requirements. Among these requirements, electrical compatibility is of critical significance. This study investigated the influences of the additive concentrations of three commercial ATFs on their electrical compatibilities and tribological performances. Two variations of each ATF with different concentrations of the original additive packages were prepared. The viscosity, electrical conductivity, permittivity, resistivity, dielectric dissipation factor, breakdown voltage, and tribological performance of the nine resulting ATFs were measured. All the ATFs were found to be electrically compatible and showed dissipative performance and sufficiently high breakdown voltage, even at increasing additive concentrations. The tribological performances of the ATFs formulated with the API (American Petroleum Institute) Group III base oils had improved wear reduction at the highest additive concentrations; the better wear performance was related to the formation of iron phosphates and polyphosphates on the worn surface.

Multifunctional MXene-based fire alarm wallpaper with sandwich-like structure for enhanced fire safety and prevention

Design and development of multifunctional fire-resistant and fire alarm wallpaper (FAW) that can simultaneously hold early fire warning function and the ability to inhibit flame propagation is urgently required to boost the fire safety of combustible materials in public security. Herein, a flexible sandwich-like and nacre-biomimetic FAW was fabricated by using renewable lignocellulose nanofibrils (LCNF) and MXene thermosensitive sensor via a vacuum-assisted alternate self-assembly method. The FAW achieved ultrasensitive fire early warning response because of the synergistic effect of the insulating LCNF layers and highly conductive MXene with hierarchical structure sandwiched between LCNF layers. Furthermore, owing to the ultrafast catalytic char formation and intumescent flame retardant effect of ammonium polyphosphate (APP), the trigger sensitivity and thermal oxidation capacity of the FAW (LCNF-15) were greatly optimized by adding 15 % APP in the LCNF layer, resulting in a superior fire alarm response (0.32 s) and a continuous alarm signal (about 3073.0 s) under a flame attack. Besides, the LCNF-15 also exhibited good flexibility, ideal cyclic warning performance, excellent heat insulation ability and strong char-forming properties in a fire. The sandwich-like strategy offers a new platform for the construction of MXene-based multifunctional FAW, which is of great value in broadly addressing the fire hazard problem of traditional wallpapers.

Pyrolysis and combustion characterisation of HDPE/APP composites via molecular dynamics and CFD simulations

Understanding and characterisation of the pyrolysis and burning behaviour of flame retardant (FR) polymers are essential towards optimising the end-product in terms of flammability, charring, toxicity and smoke reduction. This study proposes a modelling framework to study the combustion behaviour, pyrolysis kinetics and FR mechanisms of FR treated polymer composites. This numerical framework has utilised reactive molecular dynamics (MD-ReaxFF) simulations to characterise the pyrolysis kinetics, char formation and residues fragments of High-density polyethylene (HDPE) and Ammonium polyphosphate filled HDPE (HDPE/APP) composites. Through MD characterisation of the polymer breaking process, thermal degradation behaviours are described by reactions rates in Arrhenius form and subsequently imported into the computational fluid dynamics (CFD) models. The modelling framework has well-predicted the heat release rate (HRR) profiles, ignition time and combustion duration of the HDPE and HDPE/APP composites, where average relative errors less than 15% were achieved compared to thermogravimetric analysis (TGA) and cone calorimeter tests. The proposed numerical framework demonstrated the capability to capture the burning behaviour and flammability of FR treated polymer composites and identify the pyrolysis kinetics and FR mechanisms offered by the APP additives, such as dehydration and char formation.

The Influence of Soil Fertilization on the Distribution and Diversity of Phosphorus Cycling Genes and Microbes Community of Maize Rhizosphere Using Shotgun Metagenomics.

Biogeochemical cycling of phosphorus in the agro-ecosystem is mediated by soil microbes. These microbes regulate the availability of phosphorus in the soil. Little is known about the response of functional traits of phosphorus cycling microbes in soil fertilized with compost manure (derived from domestic waste and plant materials) or inorganic nitrogen fertilizers at high and low doses. We used a metagenomics investigation study to understand the changes in the abundance and distribution of microbial phosphorus cycling genes in agricultural farmlands receiving inorganic fertilizers (120 kg N/ha, 60 kg N/ha) or compost manure (8 tons/ha, 4 tons/ha), and in comparison with the control. Soil fertilization with high level of compost (Cp8) or low level of inorganic nitrogen (N1) fertilizer have nearly similar effects on the rhizosphere of maize plants in promoting the abundance of genes involved in phosphorus cycle. Genes such as ppk involved in polyphosphate formation and pstSABC (for phosphate transportation) are highly enriched in these treatments. These genes facilitate phosphorus immobilization. At a high dose of inorganic fertilizer application or low compost manure treatment, the phosphorus cycling genes were repressed and the abundance decreased. The bacterial families Bacillaceae and Carnobacteriaceae were very abundant in the high inorganic fertilizer (N2) treated soil, while Pseudonocardiaceae, Clostridiaceae, Cytophagaceae, Micromonosporaceae, Thermomonosporaceae, Nocardiopsaceae, Sphaerobacteraceae, Thermoactinomycetaceae, Planococcaceae, Intrasporangiaceae, Opitutaceae, Acidimicrobiaceae, Frankiaceae were most abundant in Cp8. Pyrenophora, Talaromyces, and Trichophyton fungi were observed to be dominant in Cp8 and Methanosarcina, Methanobrevibacter, Methanoculleus, and Methanosphaera archaea have the highest percentage occurrence in Cp8. Moreover, N2 treatment, Cenarchaeum, Candidatus Nitrososphaera, and Nitrosopumilus were most abundant among fertilized soils. Our findings have brought to light the basis for the manipulation of rhizosphere microbial communities and their genes to improve availability of phosphorus as well as phosphorus cycle regulation in agro-ecosystems.

Phosphorus Feast and Famine in Cyanobacteria: Is Luxury Uptake of the Nutrient Just a Consequence of Acclimation to Its Shortage?

To cope with fluctuating phosphorus (P) availability, cyanobacteria developed diverse acclimations, including luxury P uptake (LPU)—taking up P in excess of the current metabolic demand. LPU is underexplored, despite its importance for nutrient-driven rearrangements in aquatic ecosystems. We studied the LPU after the refeeding of P-deprived cyanobacterium Nostoc sp. PCC 7118 with inorganic phosphate (Pi), including the kinetics of Pi uptake, turnover of polyphosphate, cell ultrastructure, and gene expression. The P-deprived cells deployed acclimations to P shortage (reduction of photosynthetic apparatus and mobilization of cell P reserves). The P-starved cells capable of LPU exhibited a biphasic kinetic of the Pi uptake and polyphosphate formation. The first (fast) phase (1–2 h after Pi refeeding) occurred independently of light and temperature. It was accompanied by a transient accumulation of polyphosphate, still upregulated genes encoding high-affinity Pi transporters, and an ATP-dependent polyphosphate kinase. During the second (slow) phase, recovery from P starvation was accompanied by the downregulation of these genes. Our study revealed no specific acclimation to ample P conditions in Nostoc sp. PCC 7118. We conclude that the observed LPU phenomenon does not likely result from the activation of a mechanism specific for ample P conditions. On the contrary, it stems from slow disengagement of the low-P responses after the abrupt transition from low-P to ample P conditions.

The potential for polyphosphate metabolism in Archaea and anaerobic polyphosphate formation in Methanosarcina mazei

Inorganic polyphosphate (polyP) is ubiquitous across all forms of life, but the study of its metabolism has been mainly confined to bacteria and yeasts. Few reports detail the presence and accumulation of polyP in Archaea, and little information is available on its functions and regulation. Here, we report that homologs of bacterial polyP metabolism proteins are present across the major taxa in the Archaea, suggesting that archaeal populations may have a greater contribution to global phosphorus cycling than has previously been recognised. We also demonstrate that polyP accumulation can be induced under strictly anaerobic conditions, in response to changes in phosphate (Pi) availability, i.e. Pi starvation, followed by incubation in Pi replete media (overplus), in cells of the methanogenic archaeon Methanosarcina mazei. Pi-starved M. mazei cells increased transcript abundance of the alkaline phosphatase (phoA) gene and of the high-affinity phosphate transport (pstSCAB-phoU) operon: no increase in polyphosphate kinase 1 (ppk1) transcript abundance was observed. Subsequent incubation of Pi-starved M. mazei cells under Pi replete conditions, led to a 237% increase in intracellular polyphosphate content and a > 5.7-fold increase in ppk1 gene transcripts. Ppk1 expression in M. mazei thus appears not to be under classical phosphate starvation control.

Surface Fatigue Behavior of a WC/aC:H Thin-Film and the Tribochemical Impact of Zinc Dialkyldithiophosphate.

In wind turbine gearboxes, (near-)surface initiated fatigue is attributed to be the primary failure mechanism. In this work, the surface fatigue of a hydrogenated tungsten carbide/amorphous carbon (WC/aC:H) thin-film was tested under severe cyclic tribo-contact using polyalphaolefin (PAO) and PAO + zinc dialkyldithiophosphate (ZDDP) lubricants. The film was characterized in terms of its structure and chemistry using X-ray diffraction, analytical transmission electron microscopy, including electron energy loss spectroscopy (EELS), as well as X-ray photoelectron spectroscopy (XPS). The multilayer carbon thin-film exhibited promising surface fatigue performance showing a slight change in the hybridization state of the aC:H matrix. Dehydrogenation of the thin-film and subsequent transformation of cleaved C-H bonds to nonplanar sp2 carbon rings were inferred from EELS and XPS results. While tribo-induced changes to the aC:H matrix were not influenced by a nanometer-thick ZDDP reaction-film, the rate of oxidation of WC and its oxidation state were affected. While accelerating surface fatigue on a steel surface, the ZDDP-tribofilm protected the WC/aC:H film from surface fatigue. In contrast to the formation of polyphosphates from ZDDP molecules on steel surfaces, it appeared that on the WC/aC:H thin film surface, ZDDP molecules decompose to ZnO, suppressing the oxidative degradation of WC.

Global Sensitivity Analysis of Metabolic Models for Phosphorus Accumulating Organisms in Enhanced Biological Phosphorus Removal

The aim of this study was to identify, quantify and prioritize for the first time the sources of uncertainty in a mechanistic model describing the anaerobic-aerobic metabolism of phosphorus accumulating organisms (PAO) in enhanced biological phosphorus removal (EBPR) systems. These wastewater treatment systems play an important role in preventing eutrophication and metabolic models provide an advanced tool for improving their stability via system design, monitoring and prediction. To this end, a global sensitivity analysis was conducted using standard regression coefficients and Sobol sensitivity indices, taking into account the effect of 39 input parameters on 10 output variables. Input uncertainty was characterized with data in the literature and propagated to the output using the Monte Carlo method. The low degree of linearity between input parameters and model outputs showed that model simplification by linearization can be pursued only in very well defined circumstances. Differences between first and total-order sensitivity indices showed that variance in model predictions was due to interactions between combinations of inputs, as opposed to the direct effect of individual inputs. The major sources of uncertainty affecting the prediction of liquid phase concentrations, as well as intra-cellular glycogen and poly-phosphate was due to 64% of the input parameters. In contrast, the contribution to variance in intra-cellular PHA constituents was uniformly distributed among all inputs. In addition to the intra-cellular biomass constituents, notably PHB, PH2MV and glycogen, uncertainty with respect to input parameters directly related to anaerobic propionate uptake, aerobic poly-phosphate formation, glycogen formation and temperature contributed most to the variance of all model outputs. Based on the distribution of total-order sensitivities, characterization of the influent stream and intra-cellular fractions of PHA can be expected to significantly improve model reliability. The variance of EBPR metabolic model predictions was quantified. The means to account for this variance, with respect to each quantity of interest, given knowledge of the corresponding input uncertainties, was prescribed. On this basis, possible avenues and pre-requisite requirements to simplify EBPR metabolic models for PAO, both structurally via linearization, as well as by reduction of the number of non-influential variables were outlined.

Phosphorus starvation and luxury uptake in green microalgae revisited

Phosphorus (P) is central to storing and transferring energy and information in living cells, including those of microalgae. Many microalgal species dwelling in low P environments are naturally equipped to take up and store P whenever it becomes available through a complex phenomenon known as “luxury P uptake.” Its research is required for better understanding of the nutrient geochemical cycles in aquatic environments but also for biotechnological applications such as sequestration of nutrients from wastewater and production of algal fertilizers. Here, we report on our recent insights into luxury P uptake and polyphosphate formation originating from physiological, ultrastructural, and transcriptomic evidence. The cultures pre-starved of P and re-fed with inorganic phosphate (Pi) exhibited a bi-phasic kinetics of Pi uptake comprising fast (1–2 h after re-feeding) and slow (1–3 d after re-feeding) phases. The rate of Pi uptake in the fast phase was ca. 10 times higher than in the slow phase with an opposite trend shown for the cell division rate. The transient peak of polyphosphate accumulation was determined 2–4 h after re-feeding and coincided with the period of slow cell division and fast Pi uptake. In this phase, the microalgal cells reached the highest P content (up to 5% of dry cell weight). The P re-feeding also reversed the characteristic changes in cell lipids induced by P starvation, namely increase in the major membrane glycolipid (DGDG/MGDG) ratio and betaine lipids. These changes were reversed upon Pi re-feeding of the starved culture. Electron microscopy revealed the ordered organization of vacuolar polyphosphate indicative of the possible involvement of an enzyme (complex) in their synthesis. A candidate gene encoding a protein similar to the vacuolar transport chaperone (VTC) protein, featuring an expression pattern corresponding to polyphosphate accumulation, was revealed. Implications of the findings for efficient biocapture of phosphorus are discussed.

Thermal characterization of ammonium starch phosphate carbamates for potential applications as bio-based flame-retardants

The thermal degradation of ammonium starch phosphate carbamates (SPC) with varying degrees of substitution (DS) was analyzed using differential scanning calorimetry and thermogravimetry coupled with Fourier-transformed infrared spectroscopy. The data were analyzed with regard to the structural features of SPC and with respect to its potential flame-retardant properties. It became obvious that charring of SPC and polyphosphate formation in the condensed phase increased significantly in case of rising DS of SPC. Correspondingly, temperature mass losses and amounts of evolved decomposition products decreased noticeably in comparison with native starch. Activation temperatures of SPC markedly decreased with increasing DS and were considerably lower than decomposition temperatures of native starch. As a byproduct of SPC degradation ammonia was identified which contributes as inert gas to flame extinguishment. The results suggest that SPC represent promising candidates for a new generation of sustainable and environmentally friendly flame-retardants based on renewable resources.

Sulfuric acid baking and leaching of rare earth elements, thorium and phosphate from a monazite concentrate: Effect of bake temperature from 200 to 800 °C

Monazite, a rare earth and thorium bearing phosphate mineral, is one of the major minerals used for the production of rare earth elements. Although sulfuric acid baking is one of the main processing routes for extraction of rare earth elements from monazite, the chemistry involved is not well understood. In this study, a combination of chemical analysis and standard characterisation techniques (XRD, SEM-EDS, FT-IR and TG-DSC) was used to identify reaction processes occurring during the sulfuric acid baking of monazite between 200 and 800 °C. The effects of these reactions on the leachability of the rare earths, thorium and phosphate were also examined. It was observed that the sulfation reaction of monazite with acid was virtually complete after baking at 250 °C for 2 h, resulting in >90% solubilisation of rare earth elements, thorium and phosphate. After baking at 300 °C, a thorium phosphate type precipitate was formed during leaching, leading to a sharp decrease in extraction of thorium and phosphate, but the leaching of rare earth elements reached nearly 100%. The EDS and FT-IR analyses of this precipitate were indicative of a thorium pyrophosphate. As the bake temperature was further increased to 400–500 °C, extraction of thorium, phosphorus and the rare earth elements decreased due to formation of insoluble thorium-rare earth polyphosphates. The formation of these polyphosphates is thought to be related to dehydration of orthophosphoric acid produced in the initial reaction of monazite with sulfuric acid. Between 650 and 800 °C, monazite was partially re-formed, leading to a further decrease in rare earth extraction to 55%. The re-forming of monazite appeared to be due to a reaction between the thorium-rare earth polyphosphates and rare earth sulfates.

Solid‐State MAS NMR Study of Hydrated/Dehydrated Phosphorus‐modified ZSM‐5 Zeolite

The chemical changes of the phosphorus‐modified ZSM‐5 zeolites in hydration/dehydration processes have been studied by using the solid‐state MAS NMR spectroscopy. The identification of the chemical species of the steamed or washed zeolite could be done by analyzing the spectral changes on the solid‐state multinuclear MAS NMR spectroscopy when the zeolite was hydrated and dehydrated. It was reconfirmed that the steaming process effectively remove Al‐attached polyphosphates from the zeolite framework even though the zeolite was modified with phosphorus but the washing process did not. Dehydration process led to a dramatic change of aluminum species by breaking the aluminum‐oxygen bond in the zeolite framework and to a formation of polyphosphate attached to aluminum.