Physical volcanology, sedimentology, stratigraphy and petrochemistry of the Berry Creek metavolcanics: an Archean calc-alkaline complex, Lake of the Woods, Ontario

The steeply dipping, isoclinally folded early Precambrian (Archean) Berry Creek Metavolcanic Complex comprises primary to resedimented pyroclastic, epiclastic and autoclastic deposits. Tephra erupted from central volcanic edifices was dumped by mass flow mechanisms into peripheral volcanosedimentary depressions. Sedimentation has been essentially contemporaneous with eruption and transport of tephra. The monolithic to heterolithic tuffaceous horizons are interpreted as subaerial to subaqueous pumice and ash flows, secondary debris flows, lahars, slump deposits and turbidites. Monolithic debris flows, derived from crumble breccia and dcme talus, formed during downslope collapse and subsequent gravity flowage. Heterolithic tuff, lahars and lava flow morphologies suggest at least temporary emergence of the edifice. Local collapse may have accompanied pyroclastic volcanism. The tephra, produced by hydromagmatic to magmatic eruptions, were rapidly transported, by primary and secondary mechanisms, to a shallow littoral to deep water subaqueous fan developed upon the subjacent mafic metavolcanic platform. Deposition resulted from traction, traction carpet, and suspension sedimentation from laminar to turbulent flows. Facies mapping revealed proximal (channel to overbank) to distal facies epiclastics (greywackes, argillite) intercalated with proximal vent to medial fan facies crystal rich ash flows, debris flows, bedded tuff and shallow water to deep water lava flows. Framework and matrix support debris flows exhibit a variety of subaqueous sedimentary structures, e.g., coarse tail grading, double grading, inverse to normal grading, graded stratified pebbly horizons, erosional channels. Pelitic to psammitic AE turbidites also contain primary stru~tures, e.g., flames, load casts, dewatering pipes. Despite low to intermediate pressure greenschist to amphibolite grade metamorphism and variably penetrative deformation, relicts of pumice fragments and shards were recognized as recrystallized quartzofeldspathic pseudomorphs. The mafic to felsic metavolcanics and metasediments contain blasts of hornblende, actinolite, garnet, pistacitic epidote, staurolite, albitic plagioclase, and rarely andalusite and cordierite. The mafic metavolcanics (Adams River Bay, Black River, Kenu Lake, Lobstick Bay, Snake Bay) display _holeiitic trends with komatiitic affinities. Chemical variations are consistent with high level fractionation of olivine, plagioclase, amphibole, and later magnetite from a parental komatiite. The intermediate to felsic (64-74% Si02) metavolcanics generally exhibit calc-alkaline trends. The compositional discontinuity, defined by major and trace element diversity, can be explained by a mechanism involving two different magma sources. Application of fractionation series models are inconsistent with the observed data. The tholeiitic basalts and basaltic andesites are probably derived by low pressure fractionation of a depleted (high degree of partial melting) mantle source. The depleted (low Y, Zr) calc-alkaline metavolcanics may be produced by partial melting of a geochemically evolved source, e.g., tonalitetrondhjemite, garnet amphibolite or hydrous basalt.

Geochemistry of Rare Erath Elements and Trace Metals along the Western Continental Shelf of India

Rare earth elements have occupied an important role in marine geochemical research, particularly as used in the format of REE abundance patterns to describe the geochemical pathways in marine sedimentation and authigenesis. This study concentrates on the distribution pattern of Rare earth elements in the sediments, behavior of Eu and Ce with respect to their occurrence in multiple oxidation states. It also concentrate the depth wise variation of sediment REEs from near shore areas (30m) to deeper depths 200m) in the Arabian Sea. It includes the downcore variation of REEs and other trace elements in the sediment cores and a comparison between the REE distributions of Arabian Sea sediment with the sediments of Andaman Sea. The study gives a general introduction regarding the importance of RRE studies, its occurrence and abundance, electronic configuration, lanthanide contraction, oxidations states and REE supply to the ocean, seawater and sediments.

Geochemistry of transition, non-transition and rare-earth elements in the surficial sediments of continental shelf of Kerala and an annex to the Cochin estuarine system

The metals present in the surface sediments have high demand on a global perspective, and the main reservoir of these elements is believed to be the ocean floor. A lot of studies on metals are going on throughout the world for its quantification and exploitation. Even though, some preliminary attempts have been made in selected areas for the quantitative study of metals in the western continental shelf of India, no comprehensive work has been reported so far. The importance of this study also lies on the fact that there has not been a proper evaluation of the impact of the Great Tsunami of 2004 on the coastal areas of the south India. In View of this, an attempt has been made to address the seasonal distribution, behavior and mechanisms which control the deposition of metals in the sediments of the western continental shelf and Cochin Estuary, an annex to this coastal marine region.Surface sediment samples were collected seasonally from two subenvironemnts of southwest coast of India, (continental shelf of Kerala and Cochin estuarine system), to estimate the seasonal distribution and geochemical behavior of non-transition, transition, rare-earth elements, Th and U. Bottom water samples were also taken from each station, and analysed for temperature, salinity and dissolved oxygen, hence the response of redox sensitive elements to oxygen minimum zone can be addressed. In addition, other sedimentary parameters such as sand, silt, clay fractions, CaCO3 and organic carbon content were also estimated to evaluate the control factors on level of metals present in the sediment. The study used different environmental data analysis techniques to evaluate the distribution and behavior of elements during different seasons. This includes environmental parameters such as elemental normalisation, enrichment factor, element excess, cerium and europium anomalies and authigenic uranium.

Alkaline Proteases From Bacteria Isolated From Cochin Estuary

Microorganisms distributed in the marine and brackish environments play an important role in the decomposition of organic matter and mineralisation in the system (Seshadri and lgnacimuthu, 2002). Estuary is one of the most productive ecosystems, at the same time one among the least explored ecosystems on earth, which has immense potential as a source of potent microorganisms that produce valuable compounds particularly, enzymes such as proteases. In this scenario, it is very appropriate to embark on finding novel alkaline protease producers from the estuarine system. The area where the present investigation was carried out is a part of the extensive estuarine system of South India viz. Cochin Estuary. There is meagre knowledge regarding the microbial composition, particularly the protease producers of Cochin Estuary. Hence, the present study has been undertaken with the objective of finding novel alkaline protease producing bacteria from Cochin Estuary

Contrasting magmatic signatures in the Rairakhol and Koraput alkaline complexes, Eastern Ghats belt, India

The relation between alkaline magmatism and tectonism has been a contentious issue, particularly for the Precambrian continental regions. Alkaline complexes at the southwestern margin of Eastern Ghats belt, India, have been interpreted as rift-valley magmatism. However, those complexes occurring in granulite ensemble in the interior segments of the Eastern Ghats belt could not possibly be related to the rift-system, assumed for the western margin of the Eastern Ghats belt. Koraput complex was emplaced in a pull-apart structure, dominated by magmatic fabrics and geochemically similar to a fractionated alkaline complex, compatible with an alkalibasalt series. Rairakhol complex, on the other hand, shows dominantly solid-state deformation fabrics and geochemically similar to a fractionated calc-alkaline suite. Isotopic data for the Koraput complex indicate ca. 917 Ma alkaline magmatism from a depleted mantle source and postcrystalline thermal overprint at ca. 745 Ma, also recorded from sheared metapelitic country rocks. The calc-alkaline magmatism of the Rairakhol complex occurred around 938 Ma, from an enriched mantle source, closely following Grenvillian granulite facies imprint in the charnockitic country rocks.

Zr- AND Ba-RICH MINERALS FROM THE PONTE NOVA ALKALINE MAFIC-ULTRAMAFIC MASSIF, SOUTHEASTERN BRAZIL: INDICATION OF AN ENRICHED MANTLE SOURCE

Zirconium- and Ba-rich minerals are found in gabbroic rocks from the Ponte Nova alkaline mafic-ultramafic massif in southeastern Brazil. The unusual mineralogical assemblage includes zirconolite, baddeleyite, Ba-rich alkali feldspar, and Ba- and Ti-rich biotite. Zirconolite of the Ponte Nova massif has higher levels of Zr (up to 1.172 apfu) than those registered in other terrestrial rocks and a prominent enrichment in the light rare-earth elements. Baddeleyite contains small quantities of Hf, Ti, and Fe. The Ba-rich alkali feldspar and Ba- and Ti-rich biotite contain up to 9.25 and 7.35 wt% BaO, respectively, and the biotite contains up to 12.01 wt% TiO(2). In the different intrusions of the Ponte Nova massif, such an unusual assemblage typifies the residual magma after the crystallization of clinopyroxene and olivine from previously enriched basanitic parental magma. The different trends of enrichments in REE and Th + U found for zirconolite of the intrusions of the Ponte Nova massif provide a better understanding of the variable degrees of enrichment of incompatible elements of the distinct gabbroic bodies. A lithospheric mantle source enriched in incompatible elements by the metasomatic action of volatile-rich fluids and with the presence of phlogopite or amphibole (or both) and other minor accessory phases could explain the presence of the Zr- and Ba-rich minerals in this gabbroic massif.

Alkaline magmatism in the Amambay area, NE Paraguay: The Cerro Sarambi complex

The Early Cretaceous alkaline magmatism in the northeastern region of Paraguay (Amambay Province) is represented by stocks, plugs, dikes, and dike swarms emplaced into Carboniferous to Triassic-Jurassic sediments and Precambrian rocks. This magmatism is tectonically related to the Ponta Pora Arch, a NE-trending structural feature, and has the Cerro Sarambi and Cerro Chiriguelo carbonatite complexes as its most significant expressions. Other alkaline occurrences found in the area are the Cerro Guazu and the small bodies of Cerro Apua, Arroyo Gasory, Cerro Jhu, Cerro Tayay, and Cerro Teyu. The alkaline rocks comprise ultramafic-mafic, syenitic, and carbonatitic petrographic associations in addition to lithologies of variable composition and texture occurring as dikes; fenites are described in both carbonatite complexes. Alkali feldspar and clinopyroxene, ranging from diopside to aegirine, are the most abundant minerals, with feldspathoids (nepheline, analcime), biotite, and subordinate Ti-rich garnet; minor constituents are Fe-Ti oxides and cancrinite as the main alteration product from nepheline. Chemically, the Amambay silicate rocks are potassic to highly potassic and have miaskitic affinity, with the non-cumulate intrusive types concentrated mainly in the saturated to undersaturated areas in silica syenitic fields. Fine-grained rocks are also of syenitic affiliation or represent more mafic varieties. The carbonatitic rocks consist dominantly of calciocarbonatites. Variation diagrams plotting major and trace elements vs. SiO(2) concentration for the Cerro Sarambi rocks show positive correlations for Al(2)O(3), K(2)O, and Rb, and negative ones for TiO(2), MgO, Fe(2)O(3), CaO, P(2)O(5), and Sr, indicating that fractional crystallization played an important role in the formation of the complex. Incompatible elements normalized to primitive mantle display positive spikes for Rb, La, Pb, Sr, and Sm, and negative for Nb-Ta, P, and Ti, as these negative anomalies are considerably more pronounced in the carbonatites. Chondrite-normalized REE patterns point to the high concentration of these elements and to the strong LRE/HRE fractionation. The Amambay rocks are highly enriched in radiogenic Sr and have T(DM) model ages that vary from 1.6 to 1.1 Ga. suggesting a mantle source enriched in incompatible elements by metasomatic events in Paleo-Mesoproterozoic times. Data are consistent with the derivation of the Cerro Sarambi rocks from a parental magma of lamprophyric (minette) composition and suggest an origin by liquid immiscibility processes for the carbonatites. (C) 2011 Elsevier Ltd. All rights reserved.

Bismuth Modified Gold Microelectrode for Pb(II) Determination in Wine Using Alkaline Medium

Electrodeposition of bismuth on gold microelectrodes for determination of Pb(II) by square wave anodic stripping voltammetry (SWASV) was accomplished by an in situ procedure in alkaline solution. A linear calibration plot for Pb(II) in the concentration range 40 to 6700 nmol L(-1) (r=0.998) was obtained, the detection limit was found to be 12.5 nmol L(-1) (S/N = 3) and the relative standard deviation in Solutions containing 1 mu mol L(-1) Pb(II) was 4% (n = 12). The analytical performance of the proposed sensor wits tested by measuring the Pb(II) concentration in a wine sample. The result Was in good agreement with the one obtained by GFAAS.

Pt monolayer electrocatalysts for O-2 reduction: PdCo/C substrate-induced activity in alkaline media

We measured the activity of electrocatalysts, comprising Pt monolayers deposited on PdCo/C substrates with several Pd/Co atomic ratios, in the oxygen reduction reaction in alkaline solutions. The PdCo/C substrates have a core-shell structure wherein the Pd atoms are segregated at the particle`s surface. The electrochemical measurements were carried out using an ultrathin film rotating disk-ring electrode. Electrocatalytic activity for the O-2 reduction evaluated from the Tafel plots or mass activities was higher for Pt monolayers on PdCo/C compared to Pt/C for all atomic Pd/Co ratios we used. We ascribed the enhanced activity of these Pt monolayers to a lowering of the bond strength of oxygenated intermediates on Pt atoms facilitated by changes in the 5d-band reactivity of Pt. Density functional theory calculations also revealed a decline in the strength of PtOH adsorption due to electronic interaction between the Pt and Pd atoms. We demonstrated that very active O-2 reduction electrocatalysts can be devised containing only a monolayer Pt and a very small amount of Pd alloyed with Co in the substrate.

Allosteric modulation of pyrophosphatase activity of rat osseous plate alkaline phosphatase by magnesium ions

Pyrophosphatase activity of rat osseous plate alkaline phosphatase was studied at different concentrations of calcium and magnesium ions. with the aim of characterizing the modulation of enzyme activity by these metals. In the absence of metal ions, the enzyme hydrolysed pyrophosphate following Michaelian kinetics with a specific activity of 36.7 U/mg and K-0.5 = 88 mu M. In the presence of low concentrations (0.1 mM) of magnesium (or calcium) ions, the enzyme also exhibited Michaclian kinetics for the hydrolysis of pyrophosphate, but a significant increase in specific activity (123 U/mg) was observed. K-m values remained almost unchanged. Quite different behavior occurred in the presence of 2 mM magnesium (or calcium) ions. In addition to low-affinity sites (K-0.5 = 40 and 90 mu M, for magnesium and calcium, respectively), high-affinity sites were also observed with K-0.5 values 100-fold lower. The high-affinity sites observed in the presence of calcium ions represented about 10% of those observed for magnesium ions. This was correlated with the fact that only magnesium ions triggered conformational changes yielding a fully active enzyme. These results suggested that the enzyme could hydrolyse pyrophosphate, even at physiological concentrations (4 mu M), since magnesium concentrations are high enough to trigger conformational changes increasing the enzyme activity. A model, suggesting the involvement of magnesium ions in the hydrolysis of pyrophosphate by rat osseous plate alkaline phosphatase is proposed. (C) 1998 Published by Elsevier B.V. Ltd. All rights reserved.

Hydrothermal rare earth elements mineralization in the Barra do Itapirapua carbonatite, southern Brazil: behaviour of selected trace elements and stable isotopes (C, O)

The Bura do Itapira pua carbonatite is located in southern Brazil and belongs to the Cretaceous Ponta Grossa alkaline-carbonatitic province related to the opening of the South Atlantic. The carbonatite complex is emplaced in Proterozoic granites and is mainly composed of plutonic magnesio- to ferrocarbonatite, with smaller amounts of subvolcanic magnesiocarbonatite. Hydrothermal alteration of the carbonatite has led to the formation of quartz, apatite, fluorite, rue earth fluorocarbonates, barite and sulfides in variable proportions. Trace element data, delta(13)C and delta(18)O are presented here, with the aim of better understanding the geochemical nature of hydrothermal alteration related to rare earth elements (REE) mineralization. The non-overprinted plutonic carbonatite shows the lowest REE contents, and its primitive carbon and oxygen stable isotopic composition places it in the field of primary igneous carbonatites. Two types of hydrothermally overprinted plutonic carbonatites can be distinguished based on secondary minerals and geochemical composition. Type I contains mainly quartz, rare earth fluorocarbonates and apatite as hydrothermal secondary minerals, and has steep chondrite normalized REE patterns, with Sigma(REE+Y) of up to 3 wt.% (i.e., two orders of magnitude higher than in fresh plutonic samples). In contrast, the Type II overprint contains apatite, fluorite and barite as dominant hydrothermal minerals, and is characterized by heavy REE enrichment relative to the fresh samples, with flat chondrite normalized REE patterns. Carbon and oxygen stable isotope ratios of Types I and II are elevated (delta(18)O + 8 to + 12 parts per thousand; delta(13)C - 6 to - 2 parts per thousand) relative to the fresh samples. Hydrothermally overprinted carbonatites exposed to weathering show even higher delta(18)O values (delta(18)O 13 to 25 parts per thousand) but no additional REE enrichment. The subvolcanic carbonatite has anomalously high delta(13)C of up to + 1 parts per thousand, which suggests crustal contamination through interaction with carbonate-bearing metasediments. (C) 1999 Elsevier B.V. B.V. All rights reserved.

The late precambrian K-alkaline magmatism in the Ribeira Fold Belt: a case study of the Piracaia Pluton, State of São Paulo, SE Brazil, and its potential mineralization (Cu, Zn, Gd)

The Pluriserial Ribeira Magmatic System-590 of the Late Precambrian Ribeira Fold Belt comprises seven groups of high-K rocks of crustal or mantle origin with ages ranging between 620 and 570 Ma. One of these groups is represented by transalkaline suites akin to appinitic lamprophyres. The suites assemble one or more of following lithologies: (+/- quartz) gabbros and monzogabbros, (+/- quartz) diorites and monzodiorites, (+/- quartz) monzonites and syenites in addition to rare granites. All these rocks occur together in the Piracaia pluton, State of São Paulo. The mineralogy of the Piracaia suite comprises variable amounts of plagioclase (An 60-10), alkali-feldspars (orthoclase, microcline, albite), ortho- (Fe-hypersthene) and clinopyroxenes (augite), amphiboles (hornblende and rare late Fe-hastingsite), abundant biotite, quartz, opaques, sphene, allanite and zircon. Several magmatic pulses constructed the pluton. The Piracaia magma bulk trend evolved initially along the silica-undersaturation plane with simultaneous fractionation of accessory, mafic and felsic minerals. These are segregated in feldspar-rich cumulates. In the late stage, the evolutionary trend followed two distinct paths: one along the or-ab thermal barrier with the crystallization of syenites; the second one along the thermal valley in the or-ab-qz subsystem, producing quartz-syenites and granites. The source of the Piracaia magma was a 'vein-plus-wall-rock-system '. Together the pulses reflect increasing and decreasing participation of peridotites and mica pyroxenites, respectively, in the magmatogenic process. The magmatic pulses were stored in magma chambers, several drained by deep faults or fractures, which were successively reactivated and recharged. Each new pulse underwent mixing with earlier residual magma, followed by fractionation. During ascent through the hot and thickened post-collisional crust, the magma pulses underwent minor compositional changes by crustal contamination. The concentration of valuable elements (Cu, Zn, Gd) in the Piracaia pluton occurred during two phases of the magmatic evolution. Cu and Zn were enriched in cumulates and Gd was concentrated in residual quartz-syenitic veins. Due to their homogeneous dark colour and texture, the monzodiorites are exploited both for polished dimension stones and supports for sensitive scientific instruments. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

The hydrogen evolution reaction on codeposited Ni-hydrogen storage intermetallic particles in alkaline medium

The hydrogen evolution reaction (HER) was studied on Ni-LaNi5 and Ni-MmNi(3.4)Co(0.8)Al(0.8) electrode materials in 1 mol dm(-3) NaOH solution. The steady-state polarization curves and electrochemical impedance spectroscopy experimental data showed a pronounced improvement in HER kinetics when these electrode materials were used. The electrochemical results are in accordance with the Volmer-Heyrovsky mechanism. The kinetic results indicate a more effective improvement in the Heyrovsky step, suggesting an electrocatalytic synergistic effect of the hyper-electronic character of the Ni and the hypo-electronic character of the rare-earth element on the electrode surface. (C) 2000 International Association for Hydrogen Energy. Published by Elsevier B.V. Ltd. All rights reserved.

Exploratory study on sequestration of some essential metals by indigo carmine food dye

Indigo carmine forms a stable complex with different ions, and the stability constant of the complexes were evaluated as log K equal to 5.75; 5.00; 4.89 and 3.89 for complexes with Cu(II), Ni(II), Co(II) and Zn(II) ions, respectively, in 0.1 mol L -1 carbonate buffer solution at pH 10. The interaction between Cu(II) ions and indigo carmine (IC) in alkaline medium resulted in the formation of the Cu 2(IC) complex, measured by the spectrophotometric method, with a stoichiometric ratio between indigo carmine and metal ions of 2:1 (metal-ligand). The reported method has also been successfully tested for determination of copper in pharmaceutical compounds based on copper-gluconate without pre-treatment.