Ultra-distal tephra deposits from super-eruptions: examples from Toba, Indonesia and Taupo Volcanic Zone, New Zealand

Voluminous rhyolitic eruptions from Toba, Indonesia, and Taupo Volcanic Zone (TVZ), New Zealand, have dispersed volcanic ash over vast areas in the late Quaternary. The ~74 ka Youngest Toba Tuff (YTT) eruption deposited ash over the Bay of Bengal and the Indian subcontinent to the west. The ~340 ka Whakamaru eruption (TVZ) deposited the widespread Rangitawa Tephra, dominantly to the southeast (in addition to occurrences northwest of vent), extending across the landmass of New Zealand, and the South Pacific Ocean and Tasman Sea, with distal terrestrial exposures on the Chatham Islands. These super-eruptions involved ~2500 km^3 and ~1500 km3 of magma (dense-rock equivalent; DRE), respectively. Ultra-distal terrestrial exposures of YTT at two localities in India, Middle Son Valley, Madhya Pradesh, and Jurreru River Valley, Andhra Pradesh, at distances of >2000 km from the source caldera, show a basal ‘primary’ ashfall unit ~4 cm thick, although deposits containing reworked ash are up to ~3 m in total thickness. Exposures of Rangitawa Tephra on the Chatham Islands, >900 km from the source caldera, are ~15-30 cm thick. At more proximal localities (~200 km from source), Rangitawa Tephra is ~55-70 cm thick and characterized by a crystal-rich basal layer and normal grading. Both distal tephra deposits are characterized by very-fine ash (with high PM10 fractions) and are crystal-poor. Glass chemistry, stratigraphy and grain-size data for these distal tephra deposits are presented with comparisons of their correlation, dispersal and preservation. Using field observations, ash transport and deposition were modeled for both eruptions using a semi-analytical model (HAZMAP), with assumptions concerning average wind direction and strength during eruption, column shape and vent size. Model outputs provide new insights into eruption dynamics and better estimates of eruption volumes associ- ated with tephra fallout. Modeling based on observed YTT distal tephra thicknesses indicate a relatively low (<40 km high), very turbulent eruption column, consistent with deposition from a co-ignimbrite cloud extending over a broad region. Similarly, the Whakamaru eruption was modeled as producing a predominantly Plinian column (~45 km high), with dispersal to the southeast by strong prevailing winds. Significant ash fallout of the main dispersal direction, to the northwest of source, cannot be replicated in this modeling. The widespread dispersal of large volumes of fine ash from both eruptions may have had global environmental consequences, acutely affecting areas up to thousands of kilometers from vent.

Metal cluster expansion by addition of low valent group 14 reagents: III. Reaction of bis[bis(trimethylsilyl)methyl]tin with M3(CO)12 or its derivatives (M = Fe, Ru, or Os): the crystal and molecular structures of M3(μ-SnR2)2(CO)10(R = CH(SiMe3)2; M = Ru or Os)

The stannylene [SnR2] (R = CH(SiMe3)2) reacts in different ways with the three dodecacarbonyls of the iron triad: [Fe3(CO)12] gives [Fe2(CO)8(μ-SnR2)], [Ru3(CO)12] gives the planar pentametallic cluster [Ru3(CO)10(μ-SnR2)2], for which a full structural analysis is reported, while [Os3(CO)12] fails to react. Different products are also obtained from three nitrile derivatives: [Fe3-(CO)11(MeCN)] gives [Fe2(CO)6(μ-SnR2)2], which has a structure significantly different from that of known Fe2Sn2 clusters, [Ru3(CO)10(MeCN)2] gives the pentametallic cluster described above, while [Os3(CO)10(MeCN)2] gives the isostructural osmium analogue, which shows the unusual feature of a CO group bridging two osmium atoms.

Metal cluster expansion by addition of low-valent group 4B reagents: crystal and molecular structure of [Os3SnH2(CO)10{CH(SiMe3)2}2]; a compound with hydrogen bridging osmium and tin

Cluster expansion of [Os3H2(CO)10] with [SnR2][R = CH(SiMe3)2] take place in high yield to give [Os3SnH2(CO)10R2], the first closed triosmium–main-group metal cluster to be structurally characterized; a novel feature is the presence of a hydrogen atom bridging the tin atom and one of the osmium atoms.

Alkenyl derivatives of the metals. Oxidative addition to intermediate tin(II) alkenyls; isolation, and crystal and molecular structure of n-butyltris(triphenylethenyl)tin(IV)

Reaction of tin(II) chloride with Li(CPhCPh2) at –78 °C in diethyl ether–hexane–tetrahydrofuran affords a deep red solution whose colour fades on warming, and which we believe contains the (unstable) first dialkenyltin(II) species. The latter survives long enough at low temperatures to undergo intermolecular oxidative addition, and one such adduct leads ultimately to the formation of Sn(CPhCPh2)3Bun, which has been fully characterised including a crystal and molecular structure study. The mechanism of formation of the final product has been examined and results are reported.

Effects of addition of phenolic compounds on the acid gelation of milk

Tannic acid (0.1–1%, w/w) and gallic acid (0.3–1%, w/w) were added to skim milk prior to acidification with GDL. The acid gelation of tannic and gallic acid fortified milk had a faster gelation time in comparison with the control gel without phenolic compounds. The addition of tannic acid and gallic acid (up to 0.8%) to the milk resulted in a higher storage modulus (G′), decrease in the water mobility (T2 time) and had no significant effect on the syneresis index (SI). However, the inclusion of 1% gallic acid resulted in a significant decrease in G′, a significant increase in the SI and a wider T2 distribution. Lowering the temperature of the gels from 30 to 5 °C caused the G′ for the gels with gallic and tannic acid to increase significantly in comparison with the control, possibly due to increased hydrogen bonding in the presence of phenolic compounds

Reversible addition of CO to coordinatively unsaturated high-spin iron(II) complexes

Several new coordinatively unsaturated iron(II) complexes of the types [Fe(EN-iPr)X2] (E = P, S, Se; X = Cl, Br) and [Fe(ON-iPr)2X]X containing bidentate EN ligands based on N-(2-pyridinyl)aminophosphines as well as oxo, thio, and seleno derivatives thereof were prepared and characterized by NMR spectroscopy and X-ray crystallography. Mössbauer spectroscopy and magnetization studies confirmed their high-spin nature with magnetic moments very close to 4.9 μB, reflecting the expected four unpaired d-electrons in all these compounds. Stable low-spin carbonyl complexes of the types [Fe(PN-iPr)2(CO)X]X (X = Cl, Br) and cis-CO,cis-Br-[Fe(PN-iPr)(CO)2X2] (X = Br) were obtained by reacting cis-Fe(CO)4X2 with the stronger PN donor ligands, but not with the weaker EN donor ligands (E = O, S, Se). Furthermore, the reactivity of [Fe(PN-iPr)X2] toward CO was investigated by IR spectroscopy. Whereas at room temperature no reaction took place, at −50 °C [Fe(PN-iPr)X2] added readily CO to form, depending on the nature of X, the mono- and dicarbonyl complexes [Fe(PN-iPr)(X)2(CO)] (X = Cl) and [Fe(PN-iPr)(CO)2X2] (X = Cl, Br), respectively. In the case of X = Br, two isomeric dicarbonyl complexes, namely, cis-CO,trans-Br-[Fe(PN-iPr)(CO)2Br2] (major species) and cis-CO,cis-Br-[Fe(PN-iPr)(CO)2Br2] (minor species), are formed. The addition of CO to [Fe(PN-iPr)X2] was investigated in detail by means of DFT/B3LYP calculations. This study strongly supports the experimental findings that at low temperature two isomeric low-spin dicarbonyl complexes are formed. For kinetic reasons cis,trans-[Fe(PN-iPr)(CO)2Br2] releases CO at elevated temperature, re-forming [Fe(PN-iPr)Br2], while the corresponding cis,cis isomer is stable under these conditions.

A novel bogie design made of glass fibre reinforced plastic

This paper presents a completely new design of a bogie-frame made of glass fibre reinforced composites and its performance under various loading conditions predicted by finite element analysis. The bogie consists of two frames, with one placed on top of the other, and two axle ties connecting the axles. Each frame consists of two side arms and a transom between. The top frame is thinner and more compliant and has a higher curvature compared with the bottom frame. Variable vertical stiffness can be achieved before and after the contact between the two frames at the central section of the bogie to cope with different load levels. Finite element analysis played a very important role in the design of this structure. Stiffness and stress levels of the full scale bogie presented in this paper under various loading conditions have been predicted by using Marc provided by MSC Software. In order to verify the finite element analysis (FEA) models, a fifth scale prototype of the bogie has been made and tested under quasi-static loading conditions. Results of testing on the fifth scale bogie have been used to fine tune details like contact and friction in the fifth scale FEA models. These conditions were then applied to the full scale models. Finite element analysis results show that the stress levels in all directions are low compared with material strengths.

Modelling the structure of a polymer glass poly(methylmethacrylate) through neutron scattering experiments

Determination of the local structure of a polymer glass by scattering methods is complex due to the number of spatial and orientational correlations, both from within the polymer chain (intrachain) and between neighbouring chains (interchain), from which the scattering arises. Recently considerable advances have been made in the structural analysis of relatively simple polymers such as poly(ethylene) through the use of broad Q neutron scattering data tightly coupled to atomistic modelling procedures. This paper presents the results of an investigation into the use of these procedures for the analysis of the local structure of a-PMMA which is chemically more complex with a much greater number of intrachain structural parameters. We have utilised high quality neutron scattering data obtained using SANDALS at ISIS coupled with computer models representing both the single chain and bulk polymer system. Several different modelling approaches have been explored which encompass such techniques as Reverse Monte Carlo refinement and energy minimisation and their relative merits and successes are discussed. These different approaches highlight structural parameters which any realistic model of glassy atactic PMMA must replicate.

Effects of seed addition on beetle assemblages during the re-creation of species-rich lowland hay meadows

Species-rich lowland hay meadows are of conservation importance for both plants and invertebrates; however, they have declined in area across Europe as a result of conversion to other land uses and management intensification. The re-creation of these grasslands on ex-arable land provides a valuable approach to increasing the extent and conservation value of this threatened habitat. Over a 3-year period a replicated block design was used to test whether introducing seeds promoted the re-creation of both plant and phytophagous beetle assemblages typical of a target hay meadow. Seeds were harvested from local hay meadows, and applied to experimental plots in the form of either green hay or brush harvesting seeds. Green hay spreading achieved the greatest success in re-creating plant and phytophagous beetle assemblages. While re-creation success increased over time for both taxa, for the phytophagous beetles the greatest increase in re-creation success relative to the establishment year also occurred where green hay was applied. We also considered the phytophagous beetles in terms of functional traits that describe host plant specificity, larval feeding location and dispersal. Phytophagous beetle functional trait composition was most similar to the target hay meadow assemblage where some form of seed addition was used, i.e. hay spreading or brush harvested seeds. This study identified the importance of introducing target plant species as a mechanism to promote the re-creation of phytophagous beetle communities. Seed addition methods (e.g. green hay spreading) are crucial to successful hay meadow re-creation.

Homoleptic copper(II) and copper(I) complexes of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline. Six-coordinate copper(I) in solution

Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Cu(ClO(4))(2)center dot 6H(2)O in methanol in 3:1 M ratio at room temperature yields light green [CuL(3)](ClO(4))(2)center dot H(2)O (1). The X-ray crystal structure of the hemi acetonitrile solvate [CuL(3)](ClO(4))(2)center dot 0.5CH(3)CN has been determined which shows Jahn-Teller distortion in the CuN(6) core present in the cation [CuL(3)](2+). Complex 1 gives an axial EPR spectrum in acetonitrile-toluene glass with g(parallel to) = 2.262 (A(parallel to) = 169 x 10 (4) cm (1)) and g(perpendicular to) = 2.069. The Cu(II/I) potential in 1 in CH(2)Cl(2) at a glassy carbon electrode is 0.32 V versus NHE. This potential does not change with the addition of extra L in the medium implicating generation of a six-coordinate copper(I) species [CuL(3)](+) in solution. B3LYP/LanL2DZ calculations show that the six Cu-N bond distances in [CuL(3)](+) are 2.33, 2.25, 2.32, 2.25, 2.28 and 2.25 angstrom while the ideal Cu(I)-N bond length in a symmetric Cu(I)N(6) moiety is estimated as 2.25 angstrom. Reaction of L with Cu(CH(3)CN)(4)ClO(4) in dehydrated methanol at room temperature even in 4:1 M proportion yields [CuL(2)]ClO(4) (2). Its (1)H NMR spectrum indicates that the metal in [CuL(2)](+) is tetrahedral. The Cu(II/I) potential in 2 is found to be 0.68 V versus NHE in CH(2)Cl(2) at a glassy carbon electrode. In presence of excess L, 2 yields the cyclic voltammogram of 1. From (1)H NMR titration, the free energy of binding of L to [CuL(2)](+) to produce [CuL(3)](+) in CD(2)Cl(2) at 298 K is estimated as -11.7 (+/-0.2) kJ mol (1).

Effect of cattle urine addition on the surface emissions and subsurface concentrations of greenhouse gases in a UK peat grassland

Grazing systems represent a substantial percentage of the global anthropogenic flux of nitrous oxide (N2O) as a result of nitrogen addition to the soil. The pool of available carbon that is added to the soil from livestock excreta also provides substrate for the production of carbon dioxide (CO2) and methane (CH4) by soil microorganisms. A study into the production and emission of CO2, CH4 and N2O from cattle urine amended pasture was carried out on the Somerset Levels and Moors, UK over a three-month period. Urine-amended plots (50 g N m−2) were compared to control plots to which only water (12 mg N m−2) was applied. CO2 emission peaked at 5200 mg CO2 m−2 d−1 directly after application. CH4 flux decreased to −2000 μg CH4 m−2 d−1 two days after application; however, net CH4 flux was positive from urine treated plots and negative from control plots. N2O emission peaked at 88 mg N2O m−2 d−1 12 days after application. Subsurface CH4 and N2O concentrations were higher in the urine treated plots than the controls. There was no effect of treatment on subsurface CO2 concentrations. Subsurface N2O peaked at 500 ppm 12 days after and 1200 ppm 56 days after application. Subsurface NO3− concentration peaked at approximately 300 mg N kg dry soil−1 12 days after application. Results indicate that denitrification is the key driver for N2O release in peatlands and that this production is strongly related to rainfall events and water-table movement. N2O production at depth continued long after emissions were detected at the surface. Further understanding of the interaction between subsurface gas concentrations, surface emissions and soil hydrological conditions is required to successfully predict greenhouse gas production and emission.

Enhancing the crystallization and orientation of electrospinning poly (lactic acid) (PLLA) by combining with additives

PLLA is a thermoplastic biopolymer and can be used in industrial applications for medical and filtration applications. The brittleness of PLLA is attributed to slow crystallization rates and its glass transition temperature (Tg) is high (60 °C); for this reason, its applications are limited. The orientation, morphology, and crystal structure of the electrospun fibers was investigated by SEM, POM, DSC, FTIR, XRD, and SAXS. Combining with additives leads to a large decrease of fiber diameter, viscosity, and changes of fiber morphology and crystal structure compared to pure PLLA. DSC showed that the Tg of PLLA decreased about 15 °C and there was no change in relaxation enthalpy by the addition of plasticizer. FT-IR indicate a strong interaction between PLLA and additives; a new band appears in the PLLA blend at 1,756 cm−1 at room temperature as a crystalline band without any annealing. In addition, WAXD indicated that the intensities of the two peaks at (200/110) and (203) increased for the blend at room temperature without any annealing in comparison with PLLA; this means that PHB crystallizes in the amorphous region of PLLA. The POM experiments agree with the results from DSC, FTIR, and WAXS measurements, confirming that adding PHB results in an increase in the number of nuclei with much smaller spherulites and enhances the crystallization behavior of this material, thereby improving its potential for applications.

Addition of different fats to a carbohydrate food: impact on gastric emptying, glycaemic and satiety responses and comparison with in vitro digestion

In vitro, the addition of lipids to a carbohydrate food has been found to increase the digestibility of starch. In contrast, in vivo studies have shown that the addition of fat to a food can reduce the glycaemic response (GR). The aim of this study was to assess if delayed gastric emptying (GE) causes reduced GR with the addition of lipids to a carbohydrate food and if a relationship between GR and in vitro digestion of starch exists for high fat foods. Ten healthy volunteers were tested on five occasions after consuming pancakes containing 50 g of available carbohydrate and 202 kcal of sunflower oil, olive oil, butter, medium chain triglyceride (MCT) oil or a control containing no oil. GR was measured using fingerpick blood samples, satiety using visual analogue scales and GE using the 13C octanoic acid breath test. There was a significant difference in GR between the different pancake breakfasts (p = 0.05). The highest GR was observed following the control pancakes and the lowest following the olive oil pancakes. There were significant differences in GE half time, lag phase and ascension time (p < 0.05) between the different pancakes with the control pancakes having the shortest GE time and the MCT pancakes the longest. There was a significant difference in satiety parameters fullness (p = 0.003) and prospective consumption (p = 0.050), with satiety being lowest following the control pancakes. There was a significant inverse correlation between the GR and all satiety parameters. A significant inverse correlation (p = 0.009) was also observed between the digestibility of starch in vitro and GR in vivo. The paper indicates that the digestibility of starch in vitro does not predict the GR for high fat containing foods

Seedling response to phosphate addition and inoculation with arbuscular mycorrhizas and the implications for old-field restoration in Western Australia

We predicted that P-fertiliser residues will limit the establishment of native plant species and their mycorrhizas to old-fields in the wheat-growing region (i.e. the wheatbelt) of Western Australia. To test this prediction, we assessed the growth and P uptake of seedlings of three native plant species to phosphate addition and inoculation with arbuscular mycorrhizas (AM) in a pot study. The native plant species were Acacia acuminata Benth. (Mimosaceae), Eucalyptus loxophleba Benth. subsp. loxophleba (Myrtaceae) and Hakea preissii Meisn. (Proteaceae); and each pot contained one seedling. P was added to field soil to mimic pre-agricultural (P0), old-field (P1) and 10 times old-field (P10) soils. AM inoculant, which was a mix of Scutellospora calospora (Nicolson and Gerdemann) Walker and Sanders, Glomus intraradices Schenck and Smith and Glomus mosseae (Nicolson and Gerdemann) Gerdemann and Trappe, was added to half of the pots. After 12 weeks, the biomass and P uptake of the mycorrhizal A. acuminata were greater than those of the non-mycorrhizal plants across all P treatments. Plant biomass decreased significantly with increasing P addition, yet this species was apparently unable to suppress its mycorrhizal colonisation at high P despite this reduction in growth. In contrast, mycorrhizal and non-mycorrhizal E. loxophleba subsp. loxophleba were of a similar biomass after 12 weeks; maximum biomass was attained at intermediate (old-field) levels of P. P uptake increased with increasing P supply, beyond that required to attain maximum biomass. AM did not form on H. preissii. P uptake increased with increasing P supply for this species also. Overall, it is the apparent inability of these species to down-regulate P uptake rather than a lack of mycorrhizal symbiosis that will constrain their establishment on wheatbelt old-fields.