Phosphorus (P) fertilizer is an essential component of our food system with the majority of all mined P rock processed to make mineral fertilizers. Globally however P rock stocks are declining-both in quality and quantity-with poor P management creating a linear economic system where P is mined, globally redistributed into products and eventually discharged into the environment leading to eutrophication. To enable establishment of a circular P economy, whereby P can be recovered from waste for its industrial reuse, requires the development of effective P recovery technologies.
View Article and Find Full Text PDFIt is essential to understand the P dynamics of recycled biomaterials, like biochar derived from sewage sludge, especially with potential application as fertilizers. The objective of this study was to understand how pyrolysis affects the speciation of P in sewage sludge and thereby the effect on labile P pools and mobility of P in soil. The P speciation and lability of two sewage sludges (one biologically treated and one iron-precipitated) and their biochars (pyrolyzed at 400 °C and 600 °C) were determined by liquid state P nuclear magnetic resonance spectroscopy, X-ray absorption near edge spectroscopy, and sequential chemical extraction.
View Article and Find Full Text PDFSlow-release fertilizers (SRFs) form the core of innovative strategies in sustainable agriculture. Layered Double Hydroxides (LDH), known for their high capacity to sequester plant nutrients, especially phosphate, are emerging as promising candidates for SRF synthesis. The phosphate release properties of MgAl LDH (with a targeted Mg/Al ratio of 2.
View Article and Find Full Text PDFIn this study, cyanobacterial biochars (CBs) enriched/doped with non-metallic elements were prepared by pyrolysis of biomass amended with different N, S, and P containing compounds. Their catalytic reactivity was tested for persulfate oxidation of the antibiotic norfloxacin (NOR). N and S doping failed to improve CB catalytic reactivity, while P doping increased reactivity 5 times compared with un-doped biochar.
View Article and Find Full Text PDFStructural disorder and low crystallinity render it challenging to characterise the atomic-level structure of layered double hydroxides (LDH). We report a novel multi-step, first-principles computational workflow for the analysis of paramagnetic solid-state NMR of complex inorganic systems such as LDH, which are commonly used as catalysts and energy storage materials. A series of CO-labelled MgNiAl-LDH, ranging from 0 (MgAl-LDH) to 2 (NiAl-LDH), features three distinct eigenvalues , and of the experimental C chemical shift tensor.
View Article and Find Full Text PDFP-glycoprotein (P-gp) inhibitors, like zosuquidar, partly increase oral bioavailability of P-gp substrates, such as etoposide. Here, it was hypothesised that co-release of etoposide and zosuquidar from amorphous solid dispersions (ASDs) may further increase oral etoposide bioavailability. This was envisioned through simultaneous co-release and subsequent spatiotemporal association of etoposide and zosuquidar in the small intestinal lumen.
View Article and Find Full Text PDFP-glycoprotein (P-gp) limits the oral absorption of drug substances. Potent small molecule P-gp inhibitors (e.g.
View Article and Find Full Text PDFThe magnetic properties of the nickelalumite-type layered double hydroxides (LDH), MAl(OH)(SO)·3HO (MAl-LDH) with M = Co ( = 3/2), Ni ( = 1), or Cu ( = 1/2) were determined by a combined experimental and computational approach. They represent three new inorganic, low-dimensional magnetic systems with a defect-free, structurally ordered magnetic lattice. They exhibit no sign of magnetic ordering down to 2 K in contrast to conventional hydrotalcite LDH.
View Article and Find Full Text PDFThe variation in phosphorus (P) speciation of sewage sludge throughout three wastewater treatment plants (WWTPs) was obtained by combining sequential P extraction with optical and scanning electron microscopy (SEM), chemical analyses, powder X-ray diffraction (PXRD), and Al and P nuclear magnetic resonance (NMR) spectroscopy. The WWTPs combine chemical P removal (CPR) and enhanced biological P removal (EBPR) and were compared to understand the effect of iron (Fe) dosing with and without codosing of aluminum (Al) and thermal hydrolysis on the P speciation. P NMR showed comparable inorganic orthophosphate (ortho-P, 53-60% of total P) and organophosphate (organic-P, 37-45%) in primary sludge, whereas polyphosphate (poly-P, 23-44%) from poly-P accumulating organisms (PAOs) was mainly observed in the secondary sludge.
View Article and Find Full Text PDFPhosphorus (P) is present in activated sludge from wastewater treatment plants in the form of metal salt precipitates, extracellular polymeric substances, or bound into the biomass, for example, as intracellular polyphosphate (poly-P). Several methods for a reliable quantification of the different P-fractions have recently been developed, and this study combines them to obtain a comprehensive P mass-balance of activated sludge from four enhanced biological phosphate removal (EBPR) plants. Chemical characterization by ICP-OES and sequential P fractionation showed that chemically bound P constituted 38-69% of total P, most likely in the form of Fe, Mg, or Al minerals.
View Article and Find Full Text PDFBackground And Purpose: With the introduction of hybrid magnetic resonance linacs (MR-linac), improved imaging has enabled daily treatment adaptation. However, the use of gadolinium based contrast agents (GBCAs) is desired to further improve MR image contrast. GBCAs are in the form of a non-toxic metalorganic gadolinium complex, but toxic un-chelated aqueous gadolinium(III), Gd(aq), can be released in patients if the organic ligand is degraded by the radiation.
View Article and Find Full Text PDFP-glycoprotein inhibitors, like zosuquidar, have widely been used to study the role of P-glycoprotein in oral absorption. Still, systematic studies on the inhibitor dose-response relationship on intestinal drug permeation are lacking. In the present study, we investigated the effect of 0.
View Article and Find Full Text PDFThe synthesis and thermal degradation of MAl(OH)SO·3HO layered double hydroxides with M = Co, Ni, Cu, and Zn ("MAl-LDH") were investigated by inductively coupled plasma-optical emission spectroscopy, thermogravimetric analysis, powder X-ray diffraction, Rietveld refinement, scanning electron microscopy, scanning tunnel electron microscopy, energy-dispersive X-ray spectroscopy, and solid-state H and Al NMR spectroscopy. Following extensive synthesis optimization, phase pure CoAl- and NiAl-LDH were obtained, whereas 10-12% unreacted bayerite (Al(OH)) remained for the CuAl-LDH. The optimum synthesis conditions are hydrothermal treatment at 120 °C for 14 days (NiAl-LDH only 9 days) with MSO(aq) concentrations of 1.
View Article and Find Full Text PDFVivianite (Fe(PO)⋅8HO) is a potential phosphorus (P) recovery product from wastewater treatment plants (WWTPs). However, routine methods for quantification of vivianite bound P (vivianite-P) are needed to establish the link between vivianite formation and operating conditions, as current approaches require specialized instrumentation (Mössbauer or synchrotron). This study modified a conventional sequential P extraction protocol by insertion of an extraction step (0.
View Article and Find Full Text PDFCalcium controls important processes in fungal metabolism, such as hyphae growth, cell wall synthesis, and stress tolerance. Recently, it was reported that calcium affects polyphosphate and lipid accumulation in fungi. The purpose of this study was to assess the effect of calcium on the accumulation of lipids and polyphosphate for six oleaginous Mucoromycota fungi grown under different phosphorus/pH conditions.
View Article and Find Full Text PDFSolid State Nucl Magn Reson
December 2020
Environmental science is an interdisciplinary field, which integrates chemical, physical, and biological sciences to study environmental problems and human impact on the environment. This article highlights the use of solid-state NMR spectroscopy (SSNMR) in studies of environmental processes and remediation with examples from both laboratory studies and samples collected in the field. The contemporary topics presented include soil chemistry, environmental remediation (e.
View Article and Find Full Text PDFPotassium chromium jarosite, KCr(OH)(SO) (Cr-jarosite), is considered a promising candidate to display spin liquid behavior due to the strong magnetic frustration imposed by the crystal structure. However, the ground state magnetic properties have been debated, since Cr-jarosite is notoriously non-stoichiometric. Our study reports the magnetic properties for deuterated KCr(OD)(SO) on chemically well-defined samples, which have been characteried by a combination of powder X-ray diffraction, neutron diffraction, solid state NMR spectroscopy, and scanning electron microscopy with energy dispersive spectroscopy.
View Article and Find Full Text PDFJ Colloid Interface Sci
November 2020
Layered double hydroxides (LDH) and their magnetic composites have been intensively investigated as recyclable high-capacity phosphate sorbents but with little attention to their stability as function of pH and phosphate concentration. The stability of a FeO@SiO-MgFe LDH P sorbent as function of pH (5-11) and orthophosphate (P) concentration (1-300 mg P/L) was investigated. The composite has high adsorption capacity (approx.
View Article and Find Full Text PDF13C solid-state MAS NMR spectra of a series of paramagnetic metal acetylacetonate complexes; [VO(acac)2] (d1, S = ½), [V(acac)3] (d2, S = 1), [Ni(acac)2(H2O)2] (d8, S = 1), and [Cu(acac)2] (d9, S = ½), were assigned using modern NMR shielding calculations. This provided a reliable assignment of the chemical shifts and a qualitative insight into the hyperfine couplings. Our results show a reversal of the isotropic 13C shifts, δiso(13C), for CH3 and CO between the d1 and d2versus the d8 and d9 acetylacetonate complexes.
View Article and Find Full Text PDFIn the small intestine, P-glycoprotein (P-gp) may limit the permeability of its substrates, which lead to reduced oral absorption. To circumvent the effect of P-gp, a nanocomposite material termed montmorillonite-surfactant hybrid particles was developed. The particles consisted of montmorillonite, the P-gp-inhibiting, nonionic surfactant, polysorbate 20, and the P-gp substrate, digoxin.
View Article and Find Full Text PDFThe phase purity of a series of ZnAl(OH)SO· nHO layered double hydroxides (ZnAl-LDH) obtained from a reaction of bayerite (Al(OH)) with an excess of zinc(II) sulfate under hydrothermal conditions was investigated as a function of the reaction temperature, the duration of the hydrothermal treatment, and the zinc(II) concentration. The product quality, i.e.
View Article and Find Full Text PDFPolyphosphate (poly-P) is a major constituent in activated sludge from wastewater treatment plants with enhanced biological phosphorus removal due to poly-P synthesis by poly-P accumulating organisms where it plays an important role for recovery of phosphorus from waste water. Our aim was to develop a reliable protocol for poly-P quantification by P NMR spectroscopy. This has so far been complicated by the risks of inefficient extraction and poly-P hydrolysis in the extracts.
View Article and Find Full Text PDFLayered double hydroxides (LDHs), especially (doped) with transition metals, as well as nanohybrid and 2D materials derived from these structures, are interesting materials due to their catalytic and electrochemical properties. Their reactivity is determined by the atomic level distribution of the transition metal in the LDH cation layer, which is essential to control the design of LDHs with optimized properties. However, low crystallinity, absence of long range order, and/or isoelectronic ions often prevent atomic level structural characterization.
View Article and Find Full Text PDFA family of heterometallic Anderson-type 'wheels' of general formula [MIII2MII5(hmp)12](ClO4)4 (where MIII = Cr or Al and MII = Ni or Zn giving [Cr2Ni5] (1), [Cr2Zn5] (2), [Al2Ni5] (3) and [Al2Zn5] (4); hmpH = 2-pyridinemethanol) have been synthesised solvothermally. The metallic skeleton common to all structures describes a centred hexagon with the MIII sites disordered around the outer wheel. The structural disorder has been characterised via single crystal X-ray crystallography, 1-3D 1H and 13C solution-state NMR spectroscopy of the diamagnetic analogue (4), and solid-state 27Al MAS NMR spectroscopy of compounds (3) and (4).
View Article and Find Full Text PDFRecent advances in computational methodology allowed for first-principles calculations of the nuclear shielding tensor for a series of paramagnetic nickel(II) acetylacetonate complexes, [Ni(acac)L] with L = HO, DO, NH, ND, and PMePh have provided detailed insight into the origin of the paramagnetic contributions to the total shift tensor. This was employed for the assignment of the solid-state H and C MAS NMR spectra of these compounds. The two major contributions to the isotropic shifts are by orbital (diamagnetic-like) and contact mechanism.
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