Utilization of the three-dimensional volcano surface to understand the chemistry of multiphase systems in heterogeneous catalysis

CO hydrogenation is used as a model system to understand why multiphase catalysts are chemically important in heterogeneous catalysis. By including both adsorption and subsequent surface reactions, kinetic equations are derived with two fundamental properties, the chemisorption energies of C and O (Delta H-C and Delta H-O, respectively). By plotting the activity against Delta H-C and Delta H-O, a 3-D volcano surface is obtained. Because of the constraint between Delta H-C and Delta H-O on monophase systems, a maximum can be achieved. However, if multiphase systems are used, such a constraint can be released and the global maximum may be achieved.

Bronsted-Evans-Polanyi relation of multistep reactions and volcano curve in heterogeneous catalysis

Multistep surface processes involving a number of association reactions and desorption processes may be considered as hypothetical one-step desorption processes. Thus, heterogeneous catalytic reactions can be treated kinetically as consisting of two steps: adsorption and desorption. It is also illustrated that the hypothetical one-step desorption process follows the BEP relation. A volcano curve can be obtained from kinetic analysis by including both adsorption and desorption processes.

Under the volcano.

Malone, C.A.T., et al., Accordia Research Papers, 2001-3, 9: p. 7-21.

Before the Volcano:Reverberations of Identity on Montserrat

How is identity claimed, contested and sustained?

This book looks at retentions, reconstructions and reverberations of identity in a colonial Caribbean setting. It is an ‘uncomfortable’ and ‘impressionistic’ ethnography of life on the island of Montserrat leading up to and including the present day volcanic eruptions. It explores Montserrat’s existing colonial identity and emerging postcolonial identity drawing upon examples from local poets, calypsonians and historians; controversial development and trade union struggles; and the impact of tourism and colonialism on the island – Black Irish identity claims and the celebration and/or commemoration of St. Patrick’s Day in particular.

This book will appeal to Anthropologists, Sociologists, and Cultural Studies and Caribbean Studies scholars, as well as those involved in and concerned for the reconstruction of Montserrat the place and Mons’rat the people.

Mafic Plinian volcanism and ignimbrite emplacement at Tofua volcano, Tonga

Tofua Island is the largest emergent mafic volcano within the Tofua arc, Tonga, southwest Pacific. The volcano is dominated by a distinctive caldera averaging 4 km in diameter, containing a freshwater lake in the south and east. The latest paroxysmal (VEI 5-6) explosive volcanism includes two phases of activity, each emplacing a high-grade ignimbrite. The products are basaltic andesites with between 52 wt.% and 57 wt.% SiO(2). The first and largest eruption caused the inward collapse of a stratovolcano and produced the 'Tofua' ignimbrite and a sub-circular caldera located slightly northwest of the island's centre. This ignimbrite was deposited in a radial fashion over the entire island, with associated Plinian fall deposits up to 0.5 m thick on islands > 40 km away. Common sub-rounded and frequently cauliform scoria bombs throughout the ignimbrite attest to a small degree of marginal magma-water interaction. The common intense welding of the coarse-grained eruptive products, however, suggests that the majority of the erupted magma was hot, water-undersaturated and supplied at high rates with moderately low fragmentation efficiency and low levels of interaction with external water. We propose that the development of a water-saturated dacite body at shallow (<6 km) depth resulted in failure of the chamber roof to cause sudden evacuation of material, producing a Plinian eruption column. Following a brief period of quiescence, largescale faulting in the southeast of the island produced a second explosive phase believed to result from recharge of a chemically distinct magma depleted in incompatible elements. This similar, but smaller eruption, emplaced the 'Hokula' Ignimbrite sheet in the northeast of the island. A maximum total volume of 8 km(3) of juvenile material was erupted by these events. The main eruption column is estimated to have reached a height of similar to 12 km, and to have produced a major atmospheric injection of gas, and tephra recorded in the widespread series of fall deposits found on coral islands 40-80 km to the east (in the direction of regional upper-tropospheric winds). Radiocarbon dating of charcoal below the Tofua ignimbrite and organic material below the related fall units imply this eruption sequence occurred post 1,000 years BP. We estimate an eruption magnitude of 2.24x10(13) kg, sulphur release of 12 Tg and tentatively assign this eruption to the AD 1030 volcanic sulphate spike recorded in Antarctic ice sheet records.

Magma Evolution in the Primitive, Intra-oceanic Tonga Arc: Petrogenesis of Basaltic Andesites at Tofua Volcano

Tofua volcano is situated midway along the Tonga oceanic arc and has undergone two phases of ignimbrite-forming activity. The eruptive products are almost entirely basaltic andesites (52 center dot 5-57 wt % SiO2) with the exception of a volumetrically minor pre-caldera dacite. The suite displays a strong tholeiitic trend with K2O <1 wt %. Phenocryst assemblages typically comprise plagioclase + clinopyroxene +/- orthopyroxene with microlites of Ti-magnetite. Olivine (Fo(83-88)) is rare and believed to be dominantly antecrystic. An increase in the extent and frequency of reverse zoning in phenocrysts, sieve-textured plagioclase and the occurrence of antecrystic phases in post-caldera lavas record a shift to dynamic conditions, allowing the interaction of magma batches that were previously distinct. Pyroxene thermobarometry suggests crystallization at 950-1200 degrees C and 0 center dot 8-1 center dot 8 kbar. Volatile measurements of glassy melt inclusions indicate a maximum H2O content of 4 center dot 16 wt % H2O, and CO2-H2O saturation curves indicate that crystallization occurred at two levels, at depths of 4-5 center dot 5 km and 1 center dot 5-2 center dot 5 km. Major and trace element models suggest that the compositions of the majority of the samples represent a differentiation trend whereby the dacite was produced by 65% fractional crystallization of the most primitive basaltic andesite. Trace element models suggest that the sub-arc mantle source is the residuum of depleted Indian mid-ocean ridge basalt mantle (IDMM-1% melt), whereas radiogenic isotope data imply addition of 0 center dot 2% average Tongan sediment melt and a fluid component derived from the subducted altered Pacific oceanic crust. A horizontal array on the U-Th equiline diagram and Ra excesses of up to 500% suggest fluid addition to the mantle wedge within the last few thousand years. Time-integrated (Ra-226/Th-230) vs Sr/Th and Ba/Th fractionation models imply differentiation timescales of up to 4500 years for the dacitic magma compositions at Tofua.

Magma Evolution in the Primitive, Intra-oceanic Tonga Arc: Rapid Petrogenesis of Dacites at Fonualei Volcano

Fonualei is unusual amongst subaerial volcanoes in the Tonga arc because it has erupted dacitic vesicular lavas, tuffs and phreomagmatic deposits for the last 165 years. The total volume of dacite may approach 5 km(3) and overlies basal basaltic andesite and andesite lavas that are constrained to be less than a few millennia in age. All of the products are crystal-poor and formed from relatively low-viscosity magmas inferred to have had temperatures of 1100-1000 degrees C, 2-4 wt % H2O and oxygen fugacities 1-2 log units above the quartz-fayalite-magnetite buffer. Major and trace element data, along with Sr-Nd-Pb and U-Th-Ra isotope data, are used to assess competing models for the origin of the dacites. Positive correlations between Sc and Zr and Sr rule out evolution of the within-dacite compositional array by closed-system crystal fractionation of a single magma batch. An origin by partial melting of lower crustal amphibolites cannot reproduce these data trends or, arguably, any of the dacites either. Instead, we develop a model in which the dacites reflect mixing between two dacitic magmas, each the product of fractional crystallization of basaltic andesite magmas formed by different degrees of partial melting. Mixing was efficient because the two magmas had similar temperatures and viscosities. This is inferred to have occurred at shallow (2-6 km) depths beneath the volcano. U-Th-Ra disequilibria in the basaltic andesite and andesite indicate that the parental magmas had fluids added to their mantle source regions less than 8 kyr ago and that fractionation to the dacitic compositions took less than a few millennia. The 165 year eruption period for the dacites implies that mixing occurred on a similar timescale, possibly during ascent in conduits. The composition of the dacites renders them unsuitable candidates as contributors to average continental crust.

Tephra from andesitic Shiveluch volcano, Kamchatka, NW Pacific: chronology of explosive eruptions and geochemical fingerprinting of volcanic glass

The ~16-ka-long record of explosive eruptions from Shiveluch volcano (Kamchatka, NW Pacific) is refined using geochemical fingerprinting of tephra and radiocarbon ages. Volcanic glass from 77 prominent Holocene tephras and four Late Glacial tephra packages was analyzed by electron microprobe. Eruption ages were estimated using 113 radiocarbon dates for proximal tephra sequence. These radiocarbon dates were combined with 76 dates for regional Kamchatka marker tephra layers into a single Bayesian framework taking into account the stratigraphic ordering within and between the sites. As a result, we report ~1,700 high-quality glass analyses from Late Glacial–Holocene Shiveluch eruptions of known ages. These define the magmatic evolution of the volcano and provide a reference for correlations with distal fall deposits. Shiveluch tephras represent two major types of magmas, which have been feeding the volcano during the Late Glacial–Holocene time: Baidarny basaltic andesites and Young Shiveluch andesites. Baidarny tephras erupted mostly during the Late Glacial time (~16–12.8 ka BP) but persisted into the Holocene as subordinate admixture to the prevailing Young Shiveluch andesitic tephras (~12.7 ka BP–present). Baidarny basaltic andesite tephras have trachyandesite and trachydacite (SiO₂ < 71.5 wt%) glasses. The Young Shiveluch andesite tephras have rhyolitic glasses (SiO₂ > 71.5 wt%). Strongly calc-alkaline medium-K characteristics of Shiveluch volcanic glasses along with moderate Cl, CaO and low P₂O₅ contents permit reliable discrimination of Shiveluch tephras from the majority of other large Holocene tephras of Kamchatka. The Young Shiveluch glasses exhibit wave-like variations in SiO₂ contents through time that may reflect alternating periods of high and low frequency/volume of magma supply to deep magma reservoirs beneath the volcano. The compositional variability of Shiveluch glass allows geochemical fingerprinting of individual Shiveluch tephra layers which along with age estimates facilitates their use as a dating tool in paleovolcanological, paleoseismological, paleoenvironmental and archeological studies. Electronic tables accompanying this work offer a tool for statistical correlation of unknown tephras with proximal Shiveluch units taking into account sectors of actual tephra dispersal, eruption size and expected age. Several examples illustrate the effectiveness of the new database. The data are used to assign a few previously enigmatic wide-spread tephras to particular Shiveluch eruptions. Our finding of Shiveluch tephras in sediment cores in the Bering Sea at a distance of ~600 km from the source permits re-assessment of the maximum dispersal distances for Shiveluch tephras and provides links between terrestrial and marine paleoenvironmental records.

Larval development of the pedunculate barnacles Octolasmis angulata Aurivillius 1894 and Octolasmis cor Aurivillius 1892 (Cirripedia: Thoracica: Poecilasmatidae) from the gills of the mud crab, Scylla tranquebarica Fabricius, 1798

Detailed studies of larval development of Octolasmis angulata and Octolasmis cor are pivotal in understanding the larval morphological evolution as well as enhancing the functional ecology. Six planktotrophic naupliar stages and one non-feeding cyprid stage are documented in details for the first time for the two species of Octolasmis. Morphologically, the larvae of O. angulata and O. cor are similar in body size, setation patterns on the naupliar appendages, labrum, dorsal setae-pores, frontal horns, cyprid carapace, fronto-lateral gland pores, and lattice organs. Numbers of peculiarities were observed on the gnathobases of the antennae and mandible throughout the naupliar life-cycle. The setation pattern on the naupliar appendages are classified based on the segmentation on the naupliar appendages. The nauplius VI of both species undergoes a conspicuous change before metamorphosis into cyprid stage. The cyprid structures begin to form and modify beneath the naupliar body towards the end of stage VI. This study emphasises the importance of the pedunculate barnacle larval developmental studies not only to comprehend the larval morphological evolution but also to fill in the gaps in understanding the modification of the naupliar structures to adapt into the cyprid life-style.

Possibility of designing catalysts beyond the traditional volcano curve: A theoretical framework for multi-phase surfaces

The current theory of catalyst activity in heterogeneous catalysis is mainly obtained from the study of catalysts with mono-phases, while most catalysts in real systems consist of multi-phases, the understanding of which is far short of chemists' expectation. Density functional theory (DFT) and micro-kinetics simulations are used to investigate the activities of six mono-phase and nine bi-phase catalysts, using CO hydrogenation that is arguably the most typical reaction in heterogeneous catalysis. Excellent activities that are beyond the activity peak of traditional mono-phase volcano curves are found on some bi-phase surfaces. By analyzing these results, a new framework to understand the unexpected activities of bi-phase surfaces is proposed. Based on the framework, several principles for the design of multi-phase catalysts are suggested. The theoretical framework extends the traditional catalysis theory to understand more complex systems.

Antibacterial Activity of Peptides from the African Volcano Frog

Introduction: Cationic, α- helical antimicrobial peptides found in skin secretions of the African Volcano Frog, Xenopus amieti include magainin-AM1, peptide glycine-leucine-amide (PGLa-AM1) and caerulein-precursor fragment (CPF-AM1). Objectives: The principle objective of this study was to determine the antibacterial activity of these peptides against a range of aerobic and anaerobic and oral pathogens. Secondary objectives were to establish their lipopolysaccharide (LPS) binding activity and determine potential cytotoxic effects against host cells. Methods: Magainin-AM1, PGLa-AM1 and CPF-AM1 were assessed for their antimicrobial activity against Fusobacteriim nucleatum, Streptococcus mutans, Lactobacillus acidophilus, Enterococcus faecalis and Streptococcus milleri using a double layer radial diffusion assay. The propensity for each peptide to bind LPS was determined using an indirect ELISA. The potential cytotoxicity of the peptides against human pulp cells in vitro was determined using the 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Results: Magainin-AM1, PGLa-AM1 and CPF-AM1 displayed potent antimicrobial activity against all the bacterial pathogens tested, with Magainin-AM1 being the least effective. PGLa-AM1 was most potent against S. mutans, with a minimum inhibitory concentration (MIC) of 1.2 μM. PGLa-AM1 and CPF-AM1 were both very active against F. nucleatum with MIC values of 1.5 μM and 2.2 μM respectively. The LPS binding ability of the peptides varied depending on the bacterial source of the LPS, with PGLa-AM-1 being the most effective at binding LPS. Cytotoxicity studies revealed all three peptides lacked cytotoxic effects at the concentrations tested. Conclusions: The peptides magainin-AM1, PGLa-AM1 and CPF-AM1 from the African Volcano Frog, Xenopus amieti displayed potent antimicrobial activity and LPS binding activity against a range of oral pathogens with little cytotoxic effects. These peptides merit further studies for the development of novel therapeutics to combat common oral bacterial infections.

Antifungal Activity of Peptides From the African Volcano Frog

Background: Candidal species, particularly Candida albicans are common pathogens in the oral cavity and perioral region. Many of the manifestations of candidiasis are associated with the formation of Candida biofilms on host surfaces and/or implanted biomaterials. Biofilms are clinically important due to their increased resistance to therapeutic intervention and the ability of cells within the biofilm to withstand host immune defences.
Objectives: The present study was designed to investigate the antifungal activity of two peptides found in skin secretions of the African volcano frog (Xenopus amieti) against the type strain of C. albicans NCTC 3179.
Methods: The antifungal activity of magainin-AM1 and peptide glycine-leucine-amide (PGLa-AM1) against C. albicans NCTC 3179 was studied in both planktonic and biofilm forms. Radial diffusion assays were used to obtain the minimum inhibitory concentration (MIC) of magainin-AM1 and PGLa-AM1 against planktonic C. albicans. Time kill assays were used to determine the time dependent fungicidal action of the peptides at both 4oC and 37oC. A 96 well microtitre plate model for candidal biofilm formation was employed to study the ability of the peptides to disrupt the early biofilm development (up to 24 hours) compared with the antifungal drug fluconazole. Biofilm formation was determined quantitatively using the crystal violet assay.
Results: Both magainin-AM1 and PGLa-AM1 demonstrated inhibitory activity against Candida albicans, with MIC values of 24.3 uM and 7.5uM respectively. Time-kill assays revealed bactericidal activity of both peptides at 37oC and 4oC. Magainin-AM1 and PGLa-AM1 inhibited biofilm formation in microtitre plate assays. The peptides were particularly effective during early biofilm establishment when compared with fluconazole treatment.
Conclusions: Magainin-AM1 and PGLa-AM1 are active against C albicans in both planktonic and biofilm forms. Further testing of this peptide family against candidal biofilms is recommended.

Radiological characterization of clay mixed red mud in particular as regards its leaching features

The reuse of industrial by-products such as red mud is of great importance. In the case of the building material industry the reuse of red mud requires a cautious attitude, since the enhanced radionuclide content of red mud can have an effect on human health. The natural radionuclide content of red mud from the Ajka red mud reservoir and the clay sample from a Hungarian brick factory were determined by gamma spectrometry. It was found that maximum 27.8% red mud content can be added to fulfil the conditions of the EU-BSS. The effect of heat treatment was investigated on a red mud-clay mixture and it was found that in the case of radon and thoron exhalation the applied heat reduced remarkably the exhalation capacities. The leaching features of red mud and different mixtures were studied according to the MSZ-21470-50 Hungarian standard, the British CEN/TS 14429 standard and the Tessier sequential extraction method. The Tessier method and the MSZ-21470-50 standard are suitable for the characterization of materials; however, they do not provide enough information for waste deposition purposes. To this end, we propose using the CEN/TS 14429 method, because it is easy to use, and gives detailed information about the material's behaviour under different pH conditions, however, further measurements are necessary.