A vibrational spectroscopic study of the mineral hinsdalite (Pb,Sr)Al3(PO4)(SO4)(OH)6

The objective of this research is to determine the molecular structure of the mineral hinsdalite using vibrational spectroscopy. The mineral hinsdalite (Pb,Sr)Al3(PO4,SO4)2(OH)6 is a hydroxy phosphate-sulphate mineral belonging to the beudantite subgroup of alunites. The mineral is interesting because it contains two oxyanions, phosphate and sulphate, which is unusual. The formation of hinsdalite offers a mechanism for the removal of phosphate from the environment. The mineral has been characterised by Raman spectroscopy and infrared spectroscopy. The spectra are then related to the molecular structure of the mineral. Bands at various wavenumbers are assigned to the different vibrational modes of hinsdalite, which were then associated to the molecular structure of the mineral. Bands were primarily assigned to phosphate and sulphate stretching and bending modes. The Raman spectrum is characterised by an intense sharp band at 982 cm-1 with a component band at 997 cm-1 assigned to the ν1 (PO4)3- symmetric stretching modes. Two symmetric stretching modes for both phosphate and sulphate supported the concept of non-equivalent phosphate and sulphate units in the mineral structure. Bands in the OH stretching region enabled hydrogen bond distances to be calculated. Hinsdalite is characterised by disordered phosphate/sulphate tetrahedra and non-equivalent phosphate units are observed in the vibrational spectrum of hinsdalite.

Volcanology and petrology of submarine volcanoes of the New Hebrides island arc

The New Hebrides Island Arc, an intra-oceanic island chain in the southwest Pacific, is formed by subduction of the Indo-Australian Plate beneath the Pacific Plate. The southern end of the New Hebrides Island Arc is an ideal location to study the magmatic and tectonic interaction of an emerging island arc as this part of the island chain is less than 3 million years old. A tectonically complex island arc, it exhibits a change in relative subduction rate from ~12cm/yr to 6 cm/yr before transitioning to a left-lateral strike slip zone at its southern end. Two submarine volcanic fields, Gemini-Oscostar and Volsmar, occur at this transition from normal arc subduction to sinistral strike slip movement. Multi-beam bathymetry and dredge samples collected during the 2004 CoTroVE cruise onboard the RV Southern Surveyor help define the relationship between magmatism and tectonics, and the source for these two submarine volcanic fields. Gemini-Oscostar volcanic field (GOVF), dominated by northwest-oriented normal faults, has mature polygenetic stratovolcanoes with evidence for explosive subaqueous eruptions and homogeneous monogenetic scoria cones. Volsmar volcanic field (VVF), located 30 km south of GOVF, exhibits a conjugate set of northwest and eastwest-oriented normal faults, with two polygenetic stratovolcanoes and numerous monogenetic scoria cones. A deep water caldera provides evidence for explosive eruptions at 1500m below sea level in the VVF. Both volcanic fields are dominated by low-K island arc tholeiites and basaltic andesites with calcalkalic andesite and dacite being found only in the GOVF. Geochemical signatures of both volcanic fields continue the along-arc trend of decreasing K2O with both volcanic fields being similar to the New Hebrides central chain lavas. Lavas from both fields display a slight depletion in high field strength elements and heavy rare earth elements, and slight enrichments in large-ion lithophile elements and light rare earth elements with respect to N-MORB mantle. Sr and Nd isotope data correlate with heavy rare earth and high field strength element data to show that both fields are derived from depleted mantle. Pb isotopes define Pacific MORB mantle sources and are consistent with isotopic variation along the New Hebrides Island Arc. Pb isotopes show no evidence for sediment contamination; the subduction component enrichment is therefore a slab-derived enrichment. There is a subtle spatial variation in source chemistry which sees a northerly trend of decreasing enrichment of slab-derived fluids.

Raman spectroscopy of selected tsumcorite Pb(Zn,Fe3+)2(AsO4)2(OH,H2O) minerals –implications for arsenate accumulation

The presence of arsenic in the environment is a hazard. The accumulation of arsenate by a range of cations in the formation of minerals provides a mechanism for the accumulation of arsenate. The formation of the tsumcorite minerals is an example of a series of minerals which accumulate arsenate. There are about twelve examples in this mineral group. Raman spectroscopy offers a method for the analysis of these minerals. The structure of selected tsumcorite minerals with arsenate and sulphate anions were analysed by Raman spectroscopy. Isomorphic substitution of sulphate for arsenate is observed for gartrellite and thometzekite. A comparison is made with the sulphate bearing mineral natrochalcite. The position of the hydroxyl and water stretching vibrations are related to the strength of the hydrogen bond formed between the OH unit and the AsO43- anion. Characteristic Raman spectra of the minerals enable the assignment of the bands to specific vibrational modes.

Mechanical properties of graphene : effects of layer number, temperature and isotope

Herein the mechanical properties of graphene, including Young’s modulus, fracture stress and fracture strain have been investigated by molecular dynamics simulations. The simulation results show that the mechanical properties of graphene are sensitive to the temperature changes but insensitive to the layer numbers in the multilayer graphene. Increasing temperature exerts adverse and significant effects on the mechanical properties of graphene. However, the adverse effect produced by the increasing layer number is marginal. On the other hand, isotope substitutions in graphene play a negligible role in modifying the mechanical properties of graphene.

Modelling carbon membranes for gas and isotope separation

Molecular modelling has become a useful and widely applied tool to investigate separation and diffusion behavior of gas molecules through nano-porous low dimensional carbon materials, including quasi-1D carbon nanotubes and 2D graphene-like carbon allotropes. These simulations provide detailed, molecular level information about the carbon framework structure as well as dynamics and mechanistic insights, i.e. size sieving, quantum sieving, and chemical affinity sieving. In this perspective, we revisit recent advances in this field and summarize separation mechanisms for multicomponent systems from kinetic and equilibrium molecular simulations, elucidating also anomalous diffusion effects induced by the confining pore structure and outlining perspectives for future directions in this field.

Asymmetrically decorated, doped porous graphene as an effective membrane for hydrogen isotope separation

We propose a new route to hydrogen isotope separation which exploits the quantum sieving effect in the context of transmission through asymmetrically decorated, doped porous graphenes. Selectivities of D2 over H2 as well as rate constants are calculated based on ab initio interaction potentials for passage through pure and nitrogen functionalized porous graphene. One-sided dressing of the membrane with metal provides the critical asymmetry needed for an energetically favorable pathway.

Timing and source constraints on the relationship between mafic and felsic intrusions in the Emeiashan large igneous province

Several I- and A-type granite, syenite plutons and spatially associated, giant Fe–Ti–V deposit-bearing mafic ultramafic layered intrusions occur in the Pan–Xi(Panzhihua–Xichang) area within the inner zone of the Emeishan large igneous province (ELIP). These complexes are interpreted to be related to the Emeishan mantle plume. We present LA-ICP-MS and SIMS zircon U–Pb ages and Hf–Nd isotopic compositions for the gabbros, syenites and granites from these complexes. The dating shows that the age of the felsic intrusive magmatism (256.2 ± 3.0–259.8 ± 1.6 Ma) is indistinguishable from that of the mafic intrusive magmatism (255.4 ± 3.1–259.5 ± 2.7 Ma) and represents the final phase of a continuous magmatic episode that lasted no more than 10 Myr. The upper gabbros in the mafic–ultramafic intrusions are generally more isotopically enriched (lower eNd and eHf) than the middle and lower gabbros, suggesting that the upper gabbros have experienced a higher level of crustal contamination than the lower gabbros. The significantly positive eHf(t) values of the A-type granites and syenites (+4.9 to +10.8) are higher than those of the upper gabbros of the associated mafic intrusion, which shows that they cannot be derived by fractional crystallization of these bodies. They are however identical to those of the mafic enclaves (+7.0 to +11.4) and middle and lower gabbros, implying that they are cogenetic. We suggest that they were generated by fractionation of large-volume, plume-related basaltic magmas that ponded deep in the crust. The deep-seated magma chamber erupted in two stages: the first near a density minimum in the basaltic fractionation trend and the second during the final stage of fractionation when the magma was a low density Fe-poor, Si-rich felsic magma. The basaltic magmas emplaced in the shallowlevel magma chambers differentiated to form mafic–ultramafic layered intrusions accompanied by a small amount of crustal assimilation through roof melting. Evolved A-type granites (synenites and syenodiorites) were produced dominantly by crystallization in the deep crustal magma chamber. In contrast, the I-type granites have negative eNd(t) [-6.3 to -7.5] and eHf(t) [-1.3 to -6.7] values, with the Nd model ages (T Nd DM2) of 1.63-1.67 Ga and Hf model ages (T Hf DM2) of 1.56-1.58 Ga, suggesting that they were mainly derived from partial melting of Mesoproterozoic crust. In combination with previous studies, this study also shows that plume activity not only gave rise to reworking of ancient crust, but also significant growth of juvenile crust in the center of the ELIP.

The Tarim picrite-basalt-rhyolite suite, a Permian flood basalt from Northwest China with contrasting rhyolites produced by fractional crystallization and anatexis

We report major and trace element composition, Sr–Nd isotopic and seismological data for a picrite–basalt–rhyolite suite from the northern Tarim uplift (NTU), northwest China. The samples were recovered from 13 boreholes at depths between 5,166 and 6,333 m. The picritic samples have high MgO (14.5–16.8 wt%, volatiles included) enriched in incompatible element and have high 87Sr/86Sr and low 143Nd/144Nd isotopic ratios (εNd (t) = −5.3; Sri = 0.707), resembling the Karoo high-Ti picrites. All the basaltic samples are enriched in TiO2 (2.1–3.2 wt%, volatiles free), have high FeOt abundances (11.27–15.75 wt%, volatiles free), are enriched in incompatible elements and have high Sr and low Nd isotopic ratios (Sri = 0.7049–0.7065; εNd (t) = −4.1 to −0.4). High Nb/La ratios (0.91–1.34) of basalts attest that they are mantle-derived magma with negligible crustal contamination. The rhyolite samples can be subdivided into two coeval groups with overlapping U–Pb zircon ages between 291 ± 4 and 272 ± 2 Ma. Group 1 rhyolites are enriched in Nb and Ta, have similar Nb/La, Nb/U, and Sr–Nd isotopic compositions to the associated basalts, implying that they are formed by fractional crystallization of the basalts. Group 2 rhyolites are depleted in Nb and Ta, have low Nb/La ratios, and have very high Sr and low Nd isotopic ratios, implying that crustal materials have been extensively, if not exclusively, involved in their source. The picrite–basalt–rhyolite suite from the NTU, together with Permian volcanic rocks from elsewhere Tarim basin, constitute a Large Igneous Province (LIP) that is characterized by large areal extent, rapid eruption, OIB-type chemical composition, and eruption of high temperature picritic magma. The Early Permian magmatism, which covered an area >300,000 km2, is therefore named the Tarim Flood Basalt.

Assessment of body composition in Indian adults: comparison between dual-energy X-ray absorptiometry and isotope dilution technique

Dual-energy X-ray absorptiometry (DXA) and isotope dilution technique have been used as reference methods to validate the estimates of body composition by simple field techniques; however, very few studies have compared these two methods. We compared the estimates of body composition by DXA and isotope dilution (18O) technique in apparently healthy Indian men and women (aged 19–70 years, n 152, 48 % men) with a wide range of BMI (14–40 kg/m2). Isotopic enrichment was assessed by isotope ratio mass spectroscopy. The agreement between the estimates of body composition measured by the two techniques was assessed by the Bland–Altman method. The mean age and BMI were 37 (SD 15) years and 23·3 (SD 5·1) kg/m2, respectively, for men and 37 (SD 14) years and 24·1 (SD 5·8) kg/m2, respectively, for women. The estimates of fat-free mass were higher by about 7 (95 % CI 6, 9) %, those of fat mass were lower by about 21 (95 % CI 218,223) %, and those of body fat percentage (BF%) were lower by about 7·4 (95 % CI 28·2, 26·6) % as obtained by DXA compared with the isotope dilution technique. The Bland–Altman analysis showed wide limits of agreement that indicated poor agreement between the methods. The bias in the estimates of BF% was higher at the lower values of BF%. Thus, the two commonly used reference methods showed substantial differences in the estimates of body composition with wide limits of agreement. As the estimates of body composition are method-dependent, the two methods cannot be used interchangeably

Calculation of the oxygen isotope discrimination factor for studying plant respiration

Measurement of discrimination against 18O during dark respiration in plants is currently accepted as the only reliable method of estimating the partitioning of electrons between the cytochrome and alternative pathways. In this paper, we review the theory of the technique and its application to a gas-phase system. We extend it to include sampling effects and show that the isotope discrimination factor, D, is calculated as –dln(1 + δ)/dlnO*, where δ is isotopic composition of the substrate oxygen and O*=[O2]/[N2] in a closed chamber containing tissue respiring in the dark. It is not necessary to integrate the expression but, if the integrated form is used, the resultant regression should not be constrained through the origin. This is important since any error in D will have significant effects on the estimation of the flux of electrons through the two pathways.

Coherent phonon decay and the boron isotope effect for MgB2

Ab-initio DFT calculations for the phonon dispersion (PD) and the Phonon Density Of States (PDOS) of the two isotopic forms (10B and 11B) of MgB2 demonstrate that use of a reduced symmetry super-lattice provides an improved approximation to the dynamical, phonon-distorted P6/mmm crystal structure. Construction of phonon frequency plots using calculated values for these isotopic forms gives linear trends with integer multiples of a base frequency that change in slope in a manner consistent with the isotope effect (IE). Spectral parameters inferred from this method are similar to that determined experimentally for the pure isotopic forms of MgB2. Comparison with AlB2 demonstrates that a coherent phonon decay down to acoustic modes is not possible for this metal. Coherent acoustic phonon decay may be an important contributor to superconductivity for MgB2.

Electrocatalytic and SERS activity of Pt rich Pt-Pb nanostructures formed via the utilisation of in-situ underpotential deposition of lead

The controlled synthesis of nanostructured materials remains an ongoing area of research, especially as the size, shape and composition of nanomaterials can greatly influence their properties and applications. In this work we present the electrodeposition of highly dendritic platinum rich platinum-lead nanostructures, where lead acetate acts as an inorganic shape directing agent via underpotential deposition on the growing electrodeposit. It was found that these nanomaterials readily oxidise at potentials below monolayer oxide formation, which significantly impacts on the methanol electrooxidation reaction and correlates with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis. Additionally these materials were tested for their surface enhanced Raman scattering (SERS) activity, where the high density of sharp tips provides promise for their application as SERS substrates.

Low δ18O zircons from the Bruneau-­Jarbidge eruptive center: A key to crustal anatexis along the track of the Yellowstone hotspot

The Bruneau-Jarbidge eruptive center (BJEC) in the central Snake River Plain, Idaho, USA consists of the Cougar Point Tuff (CPT), a series of ten, high-temperature (900-1000°C) voluminous ignimbrites produced over the explosive phase of volcanism (12.8-10.5 Ma) and more than a dozen equally high-temperature rhyolite lava flows produced during the effusive phase (10.5-8 Ma). Spot analyses by ion microprobe of oxygen isotope ratios in 210 zircons demonstrate that all of the eruptive units of the BJEC are characterized by zircon δ¹⁸O values ≤ 2.5‰, thus documenting the largest low δ¹⁸O silicic volcanic province known on Earth (>10⁴ km³). There is no evidence for voluminous normal δ¹⁸O magmatism at the BJEC that precedes generation of low δ¹⁸O magmas as there is at other volcanic centers that generate low δ¹⁸O magmas such as Heise and Yellowstone. At these younger volcanic centers of the hotspot track, such low δ¹⁸O magmas represent ~45 % and ~20% respectively of total eruptive volumes. Zircons in all BJEC tuffs and lavas studied (23 units) document strong δ¹⁸O depletion (median CPT δ¹⁸OZrc = 1.0‰, post-CPT lavas = 1.5‰) with the third member of the CPT recording an excursion to minimum δ¹⁸O values (δ¹⁸OZrc= -1.8‰) in a supereruption > 2‰ lower than other voluminous low δ¹⁸O rhyolites known worldwide (δ¹⁸OWR ≤0.9 vs. 3.4‰). Subsequent units of the CPT and lavas record a progressive recovery in δ¹⁸OZrc to ~2.5‰ over a ~ 4 m.y. interval (12 to 8 Ma). We present detailed evidence of unit-to-unit systematic patterns in O isotopic zoning in zircons (i.e. direction and magnitude of Δcore-rim), spectrum of δ¹⁸O in individual units, and zircon inheritance patterns established by re-analysis of spots for U-Th-Pb isotopes by LA-ICPMS and SHRIMP. In conjunction with mineral thermometry and magma compositions, these patterns are difficult to reconcile with the well-established model for "cannibalistic" low δ¹⁸O magma genesis at Heise and Yellowstone. We present an alternative model for the central Snake River Plain using the modeling results of Leeman et al. (2008) for ¹⁸O depletion as a function of depth in a mid-upper crustal protolith that was hydrothermally altered by infiltrating meteoric waters prior to the onset of silicic magmatism. The model proposes that BJEC silicic magmas were generated in response to the propagation of a melting front, driven by the incremental growth of a vast underlying mafic sill complex, over a ~5 m.y. interval through a crustal volume in which a vertically asymmetric δ¹⁸OWR gradient had previously developed that was sharply inflected from ~ -1 to 10‰ at mid-upper crustal depths. Within the context of the model, data from BJEC zircons are consistent with incremental melting and mixing events in roof zones of magma reservoirs that accompany surfaceward advance of the coupled mafic-silicic magmatic system.