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Abstract: Global resources of heavy Rare Earth Elements (REE) are dominantly sourced from Chinese regolith-hosted ion-adsorption deposits in which the REE are inferred to be weakly adsorbed onto clay minerals. Similar deposits elsewhere might provide alternative supply for these high-tech metals, but the adsorption mechanisms remain unclear and the adsorbed state of REE to clays has never been demonstrated in situ. This study compares the mineralogy and speciation of REE in economic weathering profiles from China to prospective regoliths developed on peralkaline rocks from Madagascar. We use synchrotron X-ray absorption spectroscopy to study the distribution and local bonding environment of Y and Nd, as proxies for heavy and light REE, in the deposits. Our results show that REE are truly adsorbed as easily leachable 8- to 9-coordinated outer-sphere hydrated complexes, dominantly onto kaolinite. Hence, at the atomic level, the Malagasy clays are genuine mineralogical analogues to those currently exploited in China.

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Abstract: Fly ash represents a promising alternative source of rare earth elements (REE). However, information on REE containing mineral phases and their association with other fly ash components, vital for REE recovery from fly ash, is currently lacking. Herein, the mass fraction, distribution, crystallography and solid-state chemistry of REE, U and Th in Nigerian simulated fly ash samples were characterised using a range of laboratory and synchrotron x-ray based analytical techniques to underpin future extraction methodologies. Inductively coupled plasma mass spectrometry following full-acid digest of forty-five samples revealed recoverable average total REE content which ranged between 442 mgkg−1and 625 mgkg−1, comprising over 30 wt% of the critical REE Nd, Eu, Tb, Dy, Y and Er. These REE within the fly ash samples were found to be most frequently associated with discrete monazite, xenotime and Y-bearing zircon mineral particles, with the former the most detected, which could be beneficiated through gravity separation. Analysis of monazite particles isolated from the composite samples through a complimentary suite of analytical synchrotron radiation techniques revealed a core-shell pattern, with the shell rich in colocalised Ce, Nd and La, and the core enrich in both U and Th. Ce in monazite was found to exist in a mixed trivalent and tetravalent oxidation state, with the monazite structure amorphized due to the high temperature combustion process. Such results demonstrate the strong co-association and physical distribution of REE, U and Th within monazite in fly ash; knowledge of which can subsequently be used to optimise or develop a more selective, cost-effective and environmentally friendly solvent extraction methodology, by targeting the strongly colocalised and surface bound REE in fly ash monazite particles.

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Abstract: Mankind is facing a phosphorus (P) crisis. P recycling from anthropogenic waste is critical to close the P loop. Pyrolysis could be the ideal treatment for materials, such as sewage sludge, producing a safe, nutrient-rich biochar product while sequestering the inherent carbon (C). However, pyrolysed sewage sludge typically contains low levels of potassium (K) and plant available P making the material rather unsuitable for use as fertiliser. Here, a novel treatment was investigated to produce an optimised P and K biochar fertiliser. We doped sewage sludge with a low-cost mineral (2 and 5% potassium acetate) and pyrolysed it at 700°C. The percentage water-extractable of the total P content in biochar increased by 237-times with 5% K addition compared to the undoped biochar. After six water-extractions, all the K and 16% of P was obtained. Further optimisation is feasible through adjustments of the biochar pH or doping the feedstock with other forms of K. Using XANES and synchrotron XRF mapping, we identified highly soluble potassium hydrogen phosphate up to 200-300 µm below the biochar surface. This simple and cost-effective modification enables the use of sewage sludge as safe biochar fertiliser with tailored P availability that also supplies K, improves soil properties and sequesters C.

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Abstract: Sulfur is a key volatile element in magmatic systems that exists in many phases (e.g. melt or gas), in multiple-oxidation states (S²⁻, S⁴⁺ and S⁶⁺), and has more than one stable isotope (e.g. ³²S and ³⁴S). Therefore, by measuring S, information regarding the conditions of a magma can be acquired. The aim of this work is to investigate what S can tell us about the behaviour of late-stage lunar basaltic magmas. An analytical protocol was developed to simultaneously measure S and Cl abundances and isotopes of lunar apatite in eleven lunar basalts with nano-scale secondary ion mass spectrometry (NanoSIMS). Additionally, a method was developed to measure the oxidation state of S in apatites of five mare basalts with X-ray absorption near-edge structure (XANES) spectroscopy at the S K-edge, making it possible to compare S oxidation state and S isotopes of lunar apatite for the first time. Lunar apatites contain ~20–2,800 ppm S, with δ³⁴S values between -33.3 ± 3.8‰ and +36.4 ± 3.2‰ (2σ). The Cl abundance is ~350–7,230 ppm, with δ³⁷Cl values of +6.5‰ ± 0.9‰ to +36.5‰ ± 1.1‰ (2σ). All of the apatites have S⁶⁺/ΣS(tot) ratios of >0, with average S⁶⁺/ΣS(tot) values between 0.05 and 0.55. An absence of correlation between S and Cl isotopes suggests a lack of evolutionary relationship between S and KREEP-rich components. The direction of S isotope fractionation, negative or positive, can be explained by degassing of H₂S and SO₂ from a relatively reduced (S²⁻) or oxidized (SO₄²⁻) late-stage silicate melt, respectively. The historical existence of relatively oxidized late-stage silicate melts is also evidenced by the presence of S⁶⁺ in lunar apatite. A positive trend is apparent between S⁶⁺/ΣS(tot) and δ³⁴S which is indicative of the dependence of S isotope fractionation on the oxygen fugacity of the late-stage silicate melt.

Open Access

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Abstract: Purpose : The purpose of this study was to investigate the distribution of Ca, Fe and Zn using X-ray fluorescence in human RPE/Bruch’s membrane/choroid with and without early AMD. Methods : We used a set of unfixed frozen human retinal pigment epithelium (RPE)/choroid samples from young (n=1, female aged 34) and aged donors with (n=4, males, aged 73-78) and without (n=3, one female, aged 75-77) early AMD from Manchester Eye Tissue Repository. Using X-ray fluorescence microscopy (I18 Diamond light source, UK) with a 2 um beam, we obtained high-resolution Ca, Zn, Fe, sulphur, potassium, chloride and phosphorus maps covering areas up to 100 x 600 um2 of 30 um thick sections placed on quartz holders and scanned at room temperature Results : Calcification was observed in the 3 groups. In the 34-year old sample, sparse small Ca spherules (2x2 um2) at the RPE/Bruch’s membrane interface not colocalising with Zn or Fe. In aged samples, with and without AMD, calcified nodules within RPE cells, at RPE/Bruch’s membrane interface and within druse in AMD. Every calcified nodule colocalised with Zn. Quantification revealed two types (high Zn content, low Zn content). In aged donors without AMD, high-Zn calcified nodules with Ca concentration of 3083+1679 ppm (mean+SD) (maximum 12809+9311) and Zn 66+55 ppm (max 125+75). The average size was 27+15 um2. In aged samples with AMD, high-Zn calcified nodules with average Ca concentration of 4316+1723 ppm (max 13105+7563) and Zn 97+57 ppm (max 201+143). Size 26x10 um2. In the aged non-AMD group, the low zinc-calcification nodules contained an average Ca ppm of 915+259 (max 1475+380) and Zn 33+18 ppm (max 40+21). The average size 28x16 um2. In the AMD group, the low Zn calcified nodules average Ca ppm 1544+1450 (max 3526+5289) and average Zn ppm 47+23 (max 64+37). Average size 19x10 um2. Calcified plaques in Bruch’s membrane from aged donors with and without AMD. Some of these plaques colocalised with Zn and also Fe. Fe-loaded structures in the choriocapillaris underlying calcified nodules and plaques. Conclusions : Calcific nodules contain zinc in older eyes with and without AMD. Calcified nodules with lower amounts of Ca contained lower amounts of Zn, so the accumulation of Ca may occur in parallel to Zn. It is possible that iron-loaded structures in the choriocapillaris are macrophages.