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The study presents the first evidence of metamorphosed submarine ashes in the Edough Massif, in northeastern Algeria. It occurs below the greenschist-facies Tellian units that represent the thrusted Mesozoic to Eocene passive paleomargin of northern Africa deposited on thinned continental crust. The metamorphic complex consists of tectonically superposed units composed of gneisses (lower unit) and micaschists (upper unit). At the Cap de Garde, these units enclose an "intermediate unit" composed of micaschists and meter-thick layers of marbles, which are sometimes intercalated with amphibolites. The latter occur as discontinuous small lenses and layers. The amphibolites are parallel to the primary bedding of the marbles and the main foliation. Chemical markers and field observations indicate that they are metamorphic equivalents of basic igneous rocks. The lenticular character, low thickness and multiple intercalations with marine sediments and the unusual high lithium concentrations suggest subaqueous near-source basaltic ash-fall deposits in a marine environment. (C) 2014 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Multiple P-T-d-t paths reveal the evolution of the final Nuna assembly in northeast Australia
(2020)
The final assembly of the Mesoproterozoic supercontinent Nuna was marked by the collision of Laurentia and Australia at 1.60 Ga, which is recorded in the Georgetown Inlier of NE Australia. Here, we decipher the metamorphic evolution of this final Nuna collisional event using petrostructural analysis, major and trace element compositions of key minerals, thermodynamic modelling, and multi-method geochronology. The Georgetown Inlier is characterised by deformed and metamorphosed 1.70-1.62 Ga sedimentary and mafic rocks, which were intruded byc. 1.56 Ga old S-type granites. Garnet Lu-Hf and monazite U-Pb isotopic analyses distinguish two major metamorphic events (M1 atc. 1.60 Ga and M2 atc. 1.55 Ga), which allows at least two composite fabrics to be identified at the regional scale-c. 1.60 Ga S1 (consisting in fabrics S1a and S1b) andc. 1.55 Ga S2 (including fabrics S2a and S2b). Also, three tectono-metamorphic domains are distinguished: (a) the western domain, with S1 defined by low-P(LP) greenschist facies assemblages; (b) the central domain, where S1 fabric is preserved as medium-P(MP) amphibolite facies relicts, and locally as inclusion trails in garnet wrapped by the regionally dominant low-Pamphibolite facies S2 fabric; and (c) the eastern domain dominated by upper amphibolite to granulite facies S2 foliation. In the central domain, 1.60 GaMP-medium-T(MT) metamorphism (M1) developed within the staurolite-garnet stability field, with conditions ranging from 530-550 degrees C at 6-7 kbar (garnet cores) to 620-650 degrees C at 8-9 kbar (garnet rims), and it is associated with S1 fabric. The onset of 1.55 GaLP-high-T(HT) metamorphism (M2) is marked by replacement of staurolite by andalusite (M2a/D2a), which was subsequently pseudomorphed by sillimanite (M2b/D2b) where granite and migmatite are abundant.P-Tconditions ranged from 600 to 680 degrees C and 4-6 kbar for the M2b sillimanite stage. 1.60 Ga garnet relicts within the S2 foliation highlight the progressive obliteration of the S1 fabric by regional S2 in the central zone during peak M2 metamorphism. In the eastern migmatitic complex, partial melting of paragneiss and amphibolite occurred syn- to post-S2, at 730-770 degrees C and 6-8 kbar, and at 750-790 degrees C and 6 kbar, respectively. The pressure-temperature-deformation-time paths reconstructed for the Georgetown Inlier suggest ac. 1.60 Ga M1/D1 event recorded under greenschist facies conditions in the western domain and under medium-Pand medium-Tconditions in the central domain. This event was followed by the regional 1.56-1.54 Ga low-Pand high-Tphase (M2/D2), extensively recorded in the central and eastern domains. Decompression between these two metamorphic events is ascribed to an episode of exhumation. The two-stage evolution supports the previous hypothesis that the Georgetown Inlier preserves continental collisional and subsequent thermal perturbation associated with granite emplacement.
A new micro/mesoporous hybrid clay nanocomposite prepared from kaolinite clay, Carica papaya seeds, and ZnCl2 via calcination in an inert atmosphere is presented. Regardless of the synthesis temperature, the specific surface area of the nanocomposite material is between approximate to 150 and 300 m(2)/g. The material contains both micro- and mesopores in roughly equal amounts. X-ray diffraction, infrared spectroscopy, and solid-state nuclear magnetic resonance spectroscopy suggest the formation of several new bonds in the materials upon reaction of the precursors, thus confirming the formation of a new hybrid material. Thermogravimetric analysis/differential thermal analysis and elemental analysis confirm the presence of carbonaceous matter. The new composite is stable up to 900 degrees C and is an efficient adsorbent for the removal of a water micropollutant, 4-nitrophenol, and a pathogen, E. coli, from an aqueous medium, suggesting applications in water remediation are feasible.
Novel metal-doped bacteriostatic hybrid clay composites for point-of-use disinfection of water
(2017)
This study reports the facile microwave-assisted thermal preparation of novel metal-doped hybrid clay composite adsorbents consisting of Kaolinite clay, Carica papaya seeds and/or plantain peels (Musa paradisiaca) and ZnCl2. Fourier Transformed IR spectroscopy, X-ray diffraction, Scanning Electron Microscopy and Brunauer-Emmett-Teller (BET) analysis are employed to characterize these composite adsorbents. The physicochemical analysis of these composites suggests that they act as bacteriostatic rather than bacteriacidal agents. This bacterostactic action is induced by the ZnO phase in the composites whose amount correlates with the efficacy of the composite. The composite prepared with papaya seeds (PS-HYCA) provides the best disinfection efficacy (when compared with composite prepared with Musa paradisiaca peels-PP-HYCA) against gram-negative enteric bacteria with a breakthrough time of 400 and 700 min for the removal of 1.5 x10(6) cfu/mL S. typhi and V. cholerae from water respectively. At 10(3) cfu/mL of each bacterium in solution, 2 g of both composite adsorbents kept the levels the bacteria in effluent solutions at zero for up to 24 h. Steam regeneration of 2 g of bacteria-loaded Carica papaya prepared composite adsorbent shows a loss of ca. 31% of its capacity even after the 3rd regeneration cycle of 25 h of service time. The composite adsorbent prepared with Carica papaya seeds will be useful for developing simple point-of-use water treatment systems for water disinfection application. This composite adsorbent is comparatively of good performance and shows relatively long hydraulic contact times and is expected to minimize energy intensive traditional treatment processes.
New hybrid clay adsorbent based on kaolinite clay and Carica papaya seeds with improved cation exchange capacity (CEC), rate of heavy metal ion uptake, and adsorption capacity for heavy metal ions were prepared. The CEC of the new material is ca. 75 meq/100 g in spite of the unexpectedly low surface area (approximate to 19 m(2)/g). Accordingly, the average particle size of the hybrid clay adsorbent decreased from over 200 to 100 pm. The hybrid clay adsorbent is a highly efficient adsorbent for heavy metals. With an initial metal concentration of 1 mg/L, the hybrid clay adsorbent reduces the Cd2+, Ni2+, and Pb2+ concentration in aqueous solution to <= 4, <= 7 and <= 20 mu g/L, respectively, from the first minute to over 300 min using a fixed bed containing 2 g of adsorbent and a flow rate of approximate to 7 mL/min. These values are (with the exception of Pb2+) in line with the WHO permissible limits for heavy metal ions. In a cocktail solution of Cd2+, and Ni2+, the hybrid clay shows a reduced rate of uptake but an increased adsorption capacity. The CEC data suggest that the adsorption of Pb2+, Cd2+, and Ni2+ on the hybrid clay adsorbent is essentially due to ion exchange. This hybrid clay adsorbent is prepared from materials that are abundant and by a simple means that is sustainable, easily recovered from aqueous solution, nonbiodegradable (unlike numerous biosorbent), and easily regenerated and is a highly efficient alternative to activated carbon for water treatment.
Visible-Light-Mediated Photodynamic Water Disinfection @ Bimetallic-Doped Hybrid Clay Nanocomposites
(2019)
This study reports a new class of photocatalytic hybrid clay nanocomposites prepared from low-cost sources (kaolinite clay and Carica papaya seeds) doped with Zn and Cu salts via a solvothermal process. X-ray diffraction analysis suggests that Cu-doping and Cu/Zn-doping introduce new phases into the crystalline structure of Kaolinite clay, which is linked to the reduced band gap of kaolinite from typically between 4.9 and 8.2 eV to 2.69 eV for Cu-doped and 1.5 eV for Cu/Zn hybrid clay nanocomposites (Nisar, J.; Arhammar, C.; Jamstorp, E.; Ahuja, R. Phys. Rev. B 2011, 84, 075120). In the presence of solar light irradiation, Cu- and Cu/Zn-doped nanocomposites facilitate the electron hole pair separation. This promotes the generation of singlet oxygen which in turn improves the water disinfection efficiencies of these novel nanocomposite materials. The nanocomposite materials were further characterized using high-resolution scanning electron microscopy, fluorimetry, therrnogravimetric analysis, and Raman spectroscopy. The breakthrough times of the nanocomposites for a fixed bed mode of disinfection of water contaminated with 2.32 x 10(7) cfu/mL E. coli ATCC 25922 under solar light irradiation are 25 h for Zn-doped, 30 h for Cu-doped, and 35 h for Cu/Zn-doped nanocomposites. In the presence of multidrug and multimetal resistant strains of E. coli, the breakthrough time decreases significantly. Zn-only doped nanocomposites are not photocatalytically active. In the absence of light, the nanocomposites are still effective in decontaminating water, although less efficient than under solar light irradiation. Electrostatic interaction, metal toxicity, and release of singlet oxygen (only in the Cu-doped and Cu/Zn-doped nanocomposites) are the three disinfection mechanisms by which these nanocomposites disinfect water. A regrowth study indicates the absence of any living E. coli cells in treated water even after 4 days. These data and the long hydraulic times (under gravity) exhibited by these nanocomposites during photodisinfection of water indicate an unusually high potential of these nanocomposites as efficient, affordable, and sustainable point-of-use systems for the disinfection of water in developing countries.
The sensing potential of CuO nanoparticles synthesized via. precipitation from a water/ionic liquid precursor (ILP) mixture was investigated. The particles have a moderate surface area of 66 m(2)/g after synthesis, which decreases upon thermal treatment to below 5 m(2)/g. Transmission electron microscopy confirms crystal growth upon annealing, likely due to sintering effects. The as-synthesized particles can be used for ethanol sensing. The respective sensors show fast response and recovery times of below 10 s and responses greater than 2.3 at 100 ppm of ethanol at 200 degrees C, which is higher than any CuO-based ethanol sensor described so far.
The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer) contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble) cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.
We have earlier shown that linear poly(ethylene imine) (LPEI) is an efficient growth modifier for calcium phosphate mineralization from aqueous solution (Shkilnyy et al., Langmuir, 2008, 24 (5), 2102). The current study addresses the growth process and the reason why LPEI is such an effective additive. To that end, the solution pH and the calcium and phosphate concentrations were monitored vs. reaction time using potentiometric, complexometric, and photometric methods. The phase transformations in the precipitates and particle morphogenesis were analyzed by X-ray diffraction and transmission electron microscopy, respectively. All measurements reveal steep decreases of the pH, calcium, and phosphate concentrations along with a rapid precipitation of brushite nanoparticles early on in the reaction. Brushite transforms into hydroxyapatite (HAP) within the first 2 h, which is much faster than what is reported, for example, for calcium phosphate precipitated with poly(acrylic acid). We propose that poly(ethylene imine) acts as a proton acceptor (weak buffer), which accelerates the transformation from brushite to HAP by taking up the protons that are released from the calcium phosphate precipitate during the phase transformation.
A massive pulse of granitic magma was rapidly emplaced into the once contiguous West Antarctic and New Zealand segments of the palaeo-Pacific margin of the Gondwana supercontinent at similar to 371 Ma. In New Zealand, these Late Devonian S-type granitoids cover an areal extent of > 3400 km(2), but the tectonic setting for crustal partial melting has remained unclear because most of the exposure represents either emplacement-level, or rocks that have been reworked during Cretaceous orogenesis. New petrologic data indicate that aluminous paragneisses and orthogneisses in the Bonar Range represent a rare portion of Devonian middle crust that preserves evidence for the initiation of crustal melting. The investigated rocks outline the tail of a clockwise P-T path that involved partial melting at peak conditions (similar to 670 degrees C, 5.1 kb), deformation during the immediately following near-isothermal decompression, and then partial re-equilibration under static conditions. Syn- to post-kinematic growth of zoned monazite establishes the timing of recrystallisation to a similar to 16 Ma period that began at 373.4 +/- 4.1 Ma. This age overlaps with the initiation of regional Karamea S-type granitic magmatism. Although estimated metamorphic conditions were insufficient for large amounts of melt to have been produced from Bonar Range pelites (calculated melt volumes are <10%), they do provide evidence consistent with widespread heating and partial melting in the deeper crust. This heating episode was contemporaneous with partial melting in Fiordland (New Zealand) and West Antarctica, although Mesozoic thermal and deformational events complicate the Palaeozoic record in both those areas. Nevertheless, the apparent 1000 s km of along-strike crustal partial melting indicates that a continental-scale tectonic plate margin re-organisation took place at this time. The cause in the New Zealand segment was most likely, but not unequivocally, an extensional tectonic regime with an elevated geothermal gradient caused by conductive heating from a shallowed lithospheric mantle.