Optimising the REE-Zr-Nb potential of eudialyte and its alteration products in the Ilímaussaq complex, South Greenland

Eudialyte-group minerals are complex alkali-zirconosilicates that crystallise in peralkaline igneous rocks known as agpaitic nepheline syenites 1. They provide important unexploited resources for rare earth elements (REE) and other critical metals such as Zr, Nb and Ta1,2,3,4. Europe hosts significant eudialyte deposits in rift-related alkaline intrusions, e.g. Ilímaussaq (Greenland), Lovozero and Khibiny (Russia) and Norra Kärr (Sweden)5. With relatively high contents of the more critical heavy REE, and low U and Th contents compared to conventionally exploited REE phases, eudialyte is particularly attractive as a more sustainable source of REE.Publisher PDFNon peer reviewe

Understanding cold bias : variable response of skeletal Sr/Ca to seawater pCO2 in acclimated massive Porites corals

This work was supported by the UK Natural Environment Research Council (award NE/I022973/1).Coral skeletal Sr/Ca is a palaeothermometer commonly used to produce high resolution seasonal sea surface temperature (SST) records and to investigate the amplitude and frequency of ENSO and interdecadal climate events. The proxy relationship is typically calibrated by matching seasonal SST and skeletal Sr/Ca maxima and minima in modern corals. Applying these calibrations to fossil corals assumes that the temperature sensitivity of skeletal Sr/Ca is conserved, despite substantial changes in seawater carbonate chemistry between the modern and glacial ocean. We present Sr/Ca analyses of 3 genotypes of massive Porites spp. corals (the genus most commonly used for palaeoclimate reconstruction), cultured under seawater pCO2 reflecting modern, future (year 2100) and last glacial maximum (LGM) conditions. Skeletal Sr/Ca is indistinguishable between duplicate colonies of the same genotype cultured under the same conditions, but varies significantly in response to seawater pCO2 in two genotypes of Porites lutea, whilst Porites murrayensis is unaffected. Within P. lutea, the response is not systematic: skeletal Sr/Ca increases significantly (by 2-4%) at high seawater pCO2 relative to modern in both genotypes, and also increases significantly (by 4%) at low seawater pCO2 in one genotype. This magnitude of variation equates to errors in reconstructed SST of up to -5°C.Publisher PDFPeer reviewe

From mantle to critical zone : a review of large and giant sized deposits of the rare earth elements

MS, AF and FW acknowledge the support of the NERC SoS:RARE consortium grant (NE/M011267/1). D. Kavecsanszki acknowledges the support of a postgraduate fellowship from the College of Engineering, Mathematics and Physical Sciences at the University of Exeter.The rare earth elements are unusual when defining giant-sized ore deposits, as resources are often quoted as total rare earth oxide, but the importance of a deposit may be related to the grade for individual, or a limited group of, the elements. Taking the total REE resource, only one currently known deposit (Bayan Obo) would class as giant (>1.7×107 tonnes contained metal), but a range of others classify as large (>1.7×106 tonnes). With the exception of unclassified resource estimates from the Olympic Dam IOCG deposit, all of these deposits are related to alkaline igneous activity – either carbonatites or agpaitic nepheline syenites. The total resource in these deposits must relate to the scale of the primary igneous source, but the grade is a complex function of igneous source, magmatic crystallisation, hydrothermal modification and supergene enrichment during weathering. Isotopic data suggest that the sources conducive to the formation of large REE deposits are developed in subcontinental lithospheric mantle, enriched in trace elements either by plume activity, or by previous subduction. The reactivation of such enriched mantle domains in relatively restricted geographical areas may have played a role in the formation of some of the largest deposits (e.g. Bayan Obo). Hydrothermal activity involving fluids from magmatic to meteoric sources may result in the redistribution of the REE and increases in grade, depending on primary mineralogy and the availability of ligands. Weathering and supergene enrichment of carbonatite has played a role in the formation of the highest grade deposits at Mount Weld (Australia) and Tomtor (Russia). For the individual REE with the current highest economic value (Nd and the HREE), the boundaries for the large and giant size classes are 2 orders of magnitude lower, and deposits enriched in these metals (agpaitic systems, ion absorption deposits) may have significant economic impact in the near future.Publisher PDFPeer reviewe

Ion size effects on thermoluminescence of terbium and europium doped magnesium orthosilicate

We would like to thank the support of the Fundamental Research Funds for the Central Universities of China, the National Science Foundation of China (No. 11205134) and Beijing Higher Education Young Elite Teacher Project (YETP0640). The refurbishment of the RLTL system at St. Andrews was funded by NERC grant NE/H002715/1.Thermoluminescence (TL) and radioluminescence (RL) are reported over the temperature range 25–673 K from MgSiO:Tb and MgSiO:Eu. The dominant signals arise from the transitions within the Rare Earth (RE) dopants, with limited intensity from intrinsic or host defect sites. The Tb and Eu ions distort the lattice and alter the stability of the TL sites and the peak TL temperature scales with the Tb and Eu ion size. The larger Eu ions stabilize the trapped charges more than for the Tb, and so the Eu TL peak temperatures are ∼20% higher. There are further size effects linked to the TL driven by the volume of the upper state orbitals of the rare earth transitions. For Eu the temperatures of the TL peaks are wavelength dependent since higher excited states couple to distant traps via more extensive orbits. The same pattern of peak temperature data is encoded in RL during heating. The data imply that there are sites in which the rare earth and charge stabilizing defects are closely associated within the host lattice, and the stability of the entire complex is linked to the lattice distortions from inclusions of impurities.Publisher PDFPeer reviewe

B(OH)4- and CO32- do not compete for incorporation into aragonite in synthetic precipitations at pHtotal 8.20 and 8.41 but do compete at pHtotal 8.59

This work was supported by the UK Natural Environment Research Council (NE/S001417/1) to NA, KP, RK, MC and AF. We thank Gavin Peters, University of St Andrews, for assistance with BET analyses and Adam Kerrigan, University of York, for support with scanning electron microscopy.Coral skeletal B/Ca (effectively B/CO32–), in combination with boron isotopic composition (δ11B), has been used to reconstruct the dissolved inorganic carbon chemistry of coral calcification media and to explore the biomineralisation process and its response to ocean acidification. This approach assumes that B(OH)4−, the B species incorporated into aragonite, competes with dissolved inorganic carbon species for inclusion in the mineral lattice. In this study we precipitated aragonite from seawater in vitro under conditions that simulate the compositions of the calcification media used to build tropical coral skeletons. To deconvolve the effects of pH and [CO32–] on boron incorporation we conducted multiple experiments at constant [CO32–] but variable pH and at constant pH but variable [CO32–], both in the absence and presence of common coral skeletal amino acids. Large changes in solution [CO32–], from 1000 µmol kg−1, or in precipitation rate, have no significant effect on aragonite B/Ca at pHtotal of 8.20 and 8.41. A significant inverse relationship is observed between solution [CO32–] and aragonite B/Ca at pHtotal = 8.59. Aragonite B/Ca is positively correlated with seawater pH across precipitations conducted at multiple pH but this relationship is driven by the effect of pH on the abundance of B(OH)4– in seawater. Glutamic acid and glycine enhance the incorporation of B in aragonite but aspartic acid has no measurable effect. Normalising aragonite B/Ca to solution [B(OH)4–] creates KDB(OH)4− which do not vary significantly between pH treatments. This implies that B(OH)4– and CO32– do not compete with each other for inclusion in the aragonite lattice at pHtotal 8.20 and 8.41. Only at high pH (8.59), when [B(OH)4–] is high, do we observe evidence to suggest that the 2 anions compete to be incorporated into the lattice. These high pH conditions represent the uppermost limits reliably measured in the calcification media of tropical corals cultured under present day conditions, suggesting that skeletal B/Ca may not reflect the calcification media dissolved inorganic carbon chemistry in all modern day corals.Peer reviewe

Contrasting the effects of aspartic acid and glycine in free amino acid and peptide form on the growth rate, morphology, composition and structure of synthetic aragonites

Funding: This work was supported by the UK Natural Environment Research Council (NE/S001417/1) to NA, KP, RK, MC, and AF. Raman analyses were supported by the EPSRC Light Element Analysis Facility Grant EP/T019298/1 and EPSRC Strategic Equipment Resource Grant EP/R023751/1 at the University of St Andrews.Corals and mollusks produce aragonite skeletons and shells containing highly acidic proteins, rich in aspartic acid (Asp) and glycine (Gly). These biomolecules are pivotal in controlling biomineral formation. We explore the effects of l-Asp, Gly, and two peptides: glycyl-l-aspartic acid (Gly-Asp) and tetra-aspartic acid (Asp4) on the precipitation rate, crystal morphology, and CO3 group rotational disorder (inferred from Raman spectroscopy) in aragonite precipitated in vitro at the approximate pH, [Ca2+], and Ωar occurring in coral calcification media. All of the biomolecules, except Gly, inhibit aragonite precipitation. Biomolecules are incorporated into the aragonite and create CO3 group rotational disorder in the following order: Asp4 > Asp = Gly-Asp > Gly. Asp4 inhibits aragonite precipitation more than Asp at comparable solution concentrations, but Asp reduces aragonite precipitation more effectively than Asp4 for each Asp residue incorporated into the aragonite. At the highest solution concentration, the molar ratio of Asp4:CaCO3 in the aragonite is 1:690. We observe a significant inverse relationship between the aragonite precipitation rate and aragonite Raman spectrum ν1 peak fwhm across the entire data set. Tetra-aspartic acid inhibits aragonite precipitation at all concentrations, suggesting that the aspartic acid-rich domains of coral skeletal proteins influence biomineralization by suppressing mineral formation, thereby shaping skeletal morphology and preventing uncontrolled precipitation.Peer reviewe

The response of coral skeletal nano-structure and hardness to ocean acidification conditions

Funding: Scottish Funding Council - HR09011; UK Natural Environment Research Council - NE/I022973/1.Ocean acidification typically reduces coral calcification rates and can fundamentally alter skeletal morphology. We use atomic force microscopy (AFM) and microindentation to determine how seawater pCO2 affects skeletal structure and Vickers hardness in a Porites lutea coral. At 400 µatm, the skeletal fasciculi are composed of tightly packed bundles of acicular crystals composed of quadrilateral nanograins, approximately 80–300 nm in dimensions. We interpret high adhesion at the nanograin edges as an organic coating. At 750 µatm the crystals are less regular in width and orientation and composed of either smaller/more rounded nanograins than observed at 400 µatm or of larger areas with little variation in adhesion. Coral aragonite may form via ion-by-ion attachment to the existing skeleton or via conversion of amorphous calcium carbonate precursors. Changes in nanoparticle morphology could reflect variations in the sizes of nanoparticles produced by each crystallization pathway or in the contributions of each pathway to biomineralization. We observe no significant variation in Vickers hardness between skeletons cultured at different seawater pCO2. Either the nanograin size does not affect skeletal hardness or the effect is offset by other changes in the skeleton, e.g. increases in skeletal organic material as reported in previous studies.Publisher PDFPeer reviewe

The influence of seawater pCO2 and temperature on the amino acid composition and aragonite CO3 disorder of coral skeletons

Funding: This work was supported by the Leverhulme Trust (Research project Grant 2015-268 to NA, RK, and KP) and the UK Natural Environment Research Council (NE/G015791/1 to NA and AAF; NE/S001417/1 to NA, KP, RK, MC and AAF). The Raman microscope at the University of St. Andrews is supported by the EPSRC Light Element Analysis Facility Grant EP/T019298/1 and the EPSRC Strategic Equipment Resource Grant EP/R023751/1.Coral skeletons are composites of aragonite and biomolecules. We report the concentrations of 11 amino acids in massive Porites spp. coral skeletons cultured at two temperatures (25°C and 28°C) and three seawater pCO2 (180, 400 and 750 µatm). Coral skeletal aspartic acid/asparagine (Asx), glutamic acid/glutamine (Glx), glycine, serine and total amino acid concentrations are significantly higher at 28°C than at 25°C. Skeletal Asx, Glx, Gly, Ser, Ala, L-Thr and total amino acid are significantly lower at 180 µatm seawater pCO2 compared to 400 µatm and Ser is reduced at 180 µatm compared to 750 µatm. Concentrations of all skeletal amino acids are significantly inversely related to coral calcification rate but not to calcification media pH. Raman spectroscopy of these and additional specimens indicates that CO3 disorder in the skeletal aragonite lattice is not affected by seawater pCO2 but decreases at the higher temperature. This is contrary to observations in synthetic aragonite where disorder is positively related to the aragonite precipitation rate mediated by either increasing temperature (this study) or increasing Ω (this study and a previous report) and to the concentration of amino acid in the precipitation media (a previous report). We observe no significant relationship between structural disorder and coral calcification rate or skeletal [amino acid]. Both temperature and seawater pCO2 can significantly affect skeletal amino acid composition and further work is required to clarify how environmental change mediates disorder.Peer reviewe

Electrolytic ablation of the rat pancreas: a feasibility trial

BACKGROUND: Pancreatic cancer is a biologically aggressive disease with less than 20% of patients suitable for a "curative" surgical resection. This, combined with the poor 5-year survival indicates that effective palliative methods for symptom relief are required. Currently there are no ablative techniques to treat pancreatic cancer in clinical use. Tissue electrolysis is the delivery of a direct current between an anode and cathode to induce localised necrosis. Electrolysis has been shown to be safe and reliable in producing hepatic tissue and tumour ablation in animal models and in a limited number of patients. This study investigates the feasibility of using electrolysis to produce localised pancreatic necrosis in a healthy rat model. METHOD: Ten rats were studied in total. Eight rats were treated with variable "doses" of coulombs, and the systemic and local effects were assessed; 2 rats were used as controls. RESULTS: Seven rats tolerated the procedure well without morbidity or mortality, and one died immediately post procedure. One control rat died on induction of anaesthesia. Serum amylase and glucose were not significantly affected. CONCLUSION: Electrolysis in the rat pancreas produced localised necrosis and appears both safe, and reproducible. This novel technique could offer significant advantages for patients with unresectable pancreatic tumours. The next stage of the study is to assess pancreatic electrolysis in a pig model, prior to human pilot studies