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A new solid-state material, N-butyl pyridinium diiodido argentate(I), is synthesized using a simple and effective one-pot approach. In the solid state, the compound exhibits 1D ([AgI2](-))(n) chains that are stabilized by the N-butyl pyridinium cation. The 1D structure is further manifested by the formation of long, needle-like crystals, as revealed from electron microscopy. As the general composition is derived from metal halide-based ionic liquids, the compound has a low melting point of 100-101 degrees C, as confirmed by differential scanning calorimetry. Most importantly, the compound has a conductivity of 10(-6) S cm(-1) at room temperature. At higher temperatures the conductivity increases and reaches to 10(-4 )S cm(-1) at 70 degrees C. In contrast to AgI, however, the current material has a highly anisotropic 1D arrangement of the ionic domains. This provides direct and tuneable access to fast and anisotropic ionic conduction. The material is thus a significant step forward beyond current ion conductors and a highly promising prototype for the rational design of highly conductive ionic solid-state conductors for battery or solar cell applications.
A new solid-state material, N-butyl pyridinium diiodido argentate(I), is synthesized using a simple and effective one-pot approach. In the solid state, the compound exhibits 1D ([AgI2](-))(n) chains that are stabilized by the N-butyl pyridinium cation. The 1D structure is further manifested by the formation of long, needle-like crystals, as revealed from electron microscopy. As the general composition is derived from metal halide-based ionic liquids, the compound has a low melting point of 100-101 degrees C, as confirmed by differential scanning calorimetry. Most importantly, the compound has a conductivity of 10(-6) S cm(-1) at room temperature. At higher temperatures the conductivity increases and reaches to 10(-4 )S cm(-1) at 70 degrees C. In contrast to AgI, however, the current material has a highly anisotropic 1D arrangement of the ionic domains. This provides direct and tuneable access to fast and anisotropic ionic conduction. The material is thus a significant step forward beyond current ion conductors and a highly promising prototype for the rational design of highly conductive ionic solid-state conductors for battery or solar cell applications.
In the Gasht-Masuleh area in the Alborz Mountains, gabbroic magma intruded Palaeozoic metasediments and Mesozoic sediments and crystallised as isotropic and cumulate gabbros. LREE enrichment points to relatively low degrees of mantle melting and depletion of Ti, Nb and Ta relative to primitive mantle points to an arc related component in the magma. Clinopyroxene compositions indicate MORB to arc signatures. U–Pb zircon crystallisation ages of 99.5 ± 0.6 Ma and 99.4 ± 0.6 Ma and phlogopite 40Ar/39Ar ages of 97.1 ± 0.4 Ma, 97.5 ± 0.4 Ma, 97.1 ± 0.1 Ma, within 2σ error, indicate that gabbro intrusion occurred in the (Albian-)Cenomanian (mid-Cretaceous). As active subduction did not take place in the Cretaceous in North Iran, the small volume mafic magmatism in the Gasht-Masuleh area must be due to local, extension-related mantle melting. Melting was most likely caused by far field effects triggered by roll-back of the Neo-Tethys subducting slab. As subduction took place at a distance of ~ 400 km (present distance) from the Alborz Mountains, the observed arc geochemical signatures must be inherited from a previous subduction event and concomitant mantle metasomatism, possibly in combination with contamination of the magma by crustal material.
Lanthanide based ceria nanomaterials are important practical materials due to the redox properties that are useful in the avenues pertaining to technology and life sciences. Sub 10 nm spherical and highly monodisperse Ce1−xYbxO2−y (0.04 ≤ x ≤ 0.22) nanoparticles were synthesized by thermal decomposition, annealed separately at 773 K and 1273 K for 2 hours and characterized. Elemental mapping for Yb3+ doped ceria nanoparticles shows homogeneous distribution of Yb3+ atoms in the ceria with low Yb3+ content annealed at 773 K and 1273 K for 2 hours. However, clusters are observed for 773 K annealed ceria samples with high concentration of Yb3+. These clusters are not detected in 1273 K annealed nanomaterials. Introducing small amounts of Yb3+ ions into the ceria lattice as spectroscopic probes can provide detailed information about the atomic structure and local environments allowing the monitoring of small structural changes, such as clustering. The emission spectra observed at room temperature and at 4 K have a manifold of bands that corresponds to the 2F5/2 → 2F7/2 transition of Yb3+ ions. Some small shifts are observed in the Stark splitting pattern depending on the sample and the annealing conditions. The deconvolution by PARAFAC analysis yielded luminescence decay kinetics as well as the associated luminescence spectra of three species for each of the low Yb3+ doped ceria samples annealed at 773 K and one species for the 1273 K annealed samples. However, the ceria samples with high concentration of Yb3+ annealed at the two temperatures showed only one species with lower decay times as compared to the low Yb3+ doped ceria samples.
Efficient Removal of Tetracycline and Bisphenol A from Water with a New Hybrid Clay/TiO₂ Composite
(2023)
New TiO₂ hybrid composites were prepared fromkaolinclay, predried and carbonized biomass, and titanium tetraisopropoxideand explored for tetracycline (TET) and bisphenol A (BPA) removalfrom water. Overall, the removal rate is 84% for TET and 51% for BPA.The maximum adsorption capacities (q (m))are 30 and 23 mg/g for TET and BPA, respectively. These capacitiesare far greater than those obtained for unmodified TiO2. Increasing the ionic strength of the solution does not change theadsorption capacity of the adsorbent. pH changes only slightly changeBPA adsorption, while a pH > 7 significantly reduces the adsorptionof TET on the material. The Brouers-Sotolongo fractal modelbest describes the kinetic data for both TET and BPA adsorption, predictingthat the adsorption process occurs via a complex mechanism involvingvarious forces of attraction. Temkin and Freundlich isotherms, whichbest fit the equilibrium adsorption data for TET and BPA, respectively,suggest that adsorption sites are heterogeneous in nature. Overall,the composite materials are much more effective for TET removal fromaqueous solution than for BPA. This phenomenon is assigned to a differencein the TET/adsorbent interactions vs the BPA/adsorbent interactions:the decisive factor appears to be favorable electrostatic interactionsfor TET yielding a more effective TET removal.
Eight d-metal-containing N-butylpyridinium ionic liquids (ILs) with the nominal composition (C4Py)2[Ni0.5M0.5Cl4] or (C4Py)2[Zn0.5M0.5Cl4] (M = Cu, Co, Mn, Ni, Zn; C4Py = N-butylpyridinium) were synthesized, characterized, and investigated for their optical properties. Single crystal and powder X-ray analysis shows that the compounds are isostructural to existing examples based on other d-metal ions. Inductively coupled plasma optical emission spectroscopy measurements confirm that the metal/metal ratio is around 50 : 50. UV-Vis spectroscopy shows that the optical absorption can be tuned by selection of the constituent metals. Moreover, the compounds can act as an optical sensor for the detection of gases such as ammonia as demonstrated via a simple prototype setup.
Eight d-metal-containing N-butylpyridinium ionic liquids (ILs) with the nominal composition (C4Py)2[Ni0.5M0.5Cl4] or (C4Py)2[Zn0.5M0.5Cl4] (M = Cu, Co, Mn, Ni, Zn; C4Py = N-butylpyridinium) were synthesized, characterized, and investigated for their optical properties. Single crystal and powder X-ray analysis shows that the compounds are isostructural to existing examples based on other d-metal ions. Inductively coupled plasma optical emission spectroscopy measurements confirm that the metal/metal ratio is around 50 : 50. UV-Vis spectroscopy shows that the optical absorption can be tuned by selection of the constituent metals. Moreover, the compounds can act as an optical sensor for the detection of gases such as ammonia as demonstrated via a simple prototype setup.
Fifteen N-butylpyridinium salts - five monometallic [C4Py](2)[MBr4] and ten bimetallic [C4Py](2)[(M0.5M0.5Br4)-M-a-Br-b] (M=Co, Cu, Mn, Ni, Zn) - were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 degrees C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10(-5) and 10(-6) S cm(-1). At elevated temperatures, the conductivities reach up to 10(-4) S cm(-1) at 70 degrees C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs.
The Shanderman lamprophyre dykes crop out in the western part of the Alborz Mountains (Talesh).
These rocks are classified as camptonites, composed of primary olivine, Ti-rich diopside, kaersutite, biotite, plagioclase, K-feldspar, and minor Ti-rich spinels, magnetite, pentlandite-pyrrhotite/chalcopyrite, and powellite-scheelite. Secondary analcime-wairakite, serpentines, and prehnite are common minor minerals within the studied rocks.
Olivine, Ti-rich diopside, spinel, and amphibole show distinct chemical zoning. Spinels display a core-to-rim decrease in Cr2O3, MgO, and Al2O3 concentrations and an increase in TiO2 and FeOT (total Fe as FeO), reflecting the oxidation state increase due to hydrothermal fluid influx. Low SiO2 contents (< 42 wt%), high MgO (12.44 to 13.98 wt%), and Fe2O3T (12.76 to 13.43 wt%), Cr (318-537 mu g/g) and Ni (231-327 mu g/g) contents indicate the ultrabasic nature of the rocks.
The samples show potassic character (2.1-2.8 wt% K2O), along with elevated LREE and LILE, and also exhibit minor positive Eu anomalies (Eu/Eu* = 1.09 to 1.20).
Olivine-spinel geothermometry indicates a maximum crystallization temperature of 1227 degrees C (ave. 988 degrees C +/- 65 degrees C).
Exsolution of pentlandite-pyrrhotite/chalcopyrite solid solutions occurred during magma cooling and crystallization. At lower temperatures, analcime-wairakite and prehnite partially replaced plagioclases.
The geochemical modeling of the rocks indicates the Shanderman lamprophyre magmas were derived from low-grade melting (< 5%) of amphibole-bearing garnet lherzolite source without or with very few phlogopites.
The primary magma of Shanderman lamprophyres was derived from a depth of similar to 135 km by partial melting of a metasomatized mantle source in a post-collisional environment.
The present work gives a detailed analysis of the metamorphic and structural evolution of the back-arc portion of the Famatinian Orogen exposed in the southern Sierra de Aconquija (Cuesta de La Chilca segment) in the Sierras Pampeanas Orientales (Eastern Pampean Sierras). The Pampeanas Orientales include from north to south the Aconquija, Ambato and Ancasti mountains. They are mainly composed of middle to high grade metasedimentary units and magmatic rocks.
At the south end of the Sierra de Aconquija, along an east to west segment extending over nearly 10 km (Cuesta de La Chilca), large volumes of metasedimentary rocks crop out. The eastern metasediments were defined as members of the El Portezuelo Metamorphic-Igneous Complex (EPMIC) or Eastern block and the western ones relate to the Quebrada del Molle Metamorphic Complex (QMMC) or Western block. The two blocks are divided by the La Chilca Shear Zone, which is reactivated as the Rio Chanarito fault.
The EPMIC, forming the hanging wall, is composed of schists, gneisses and rare amphibolites, calc- silicate schists, marbles and migmatites. The rocks underwent multiple episodes of deformation and a late high strain-rate episode with gradually increasing mylonitization to the west. Metamorphism progrades from a M-1 phase to the peak M-3, characterized by the reactions: Qtz + Pl + Bt +/- Ms -> Grt + Bt(2) + Pl(2) +/- Sil +/- Kfs, Qtz + Bt + Sil -> Crd + Kfs and Qtz + Grt + Sil -> Crd. The M-3 assemblage is coeval with the dominant foliation related to a third deformational phase (D-3).
The QMMC, forming the foot wall, is made up of fine-grained banded quartz - biotite schists with quartz veins and quartz-feldspar-rich pegmatites. To the east, schists are also overprinted by mylonitization. The M-3 peak assemblage is quartz + biotite + plagioclase +/- garnet +/- sillimanite +/- muscovite +/- ilmenite +/- magnetite +/- apatite.
The studied segment suffered multiphase deformation and metamorphism. Some of these phases can be correlated between both blocks. D-1 is locally preserved in scarce outcrops in the EPMIC but is the dominant in the QMMC, where S-1 is nearly parallel to S-0. In the EPMIC, D-2 is represented by the S-2 foliation, related to the F-2 folding that overprints S-1, with dominant strike NNW - SSE and high angles dip to the E. D-3 in the EPMIC have F-3 folds with axis oblique to S-2; the S-3 foliation has striking NW - SE dipping steeply to the E or W and develops interference patterns. In the QMMC, S-2 (D-2) is a discontinuous cleavage oblique to S-1 and transposed by S-3 (D-3), subparallel to S-1. Such structures in the QMMC developed at subsolidus conditions and could be correlated to those of the EPMIC, which formed under higher P-T conditions. The penetrative deformation D-2 in the EPMIC occurred during a prograde path with syntectonic growth of garnet reaching P-T conditions of 640 degrees C and 0.54 GPa in the EPMIC. This stage was followed by a penetrative deformation D-3 with syn-kinematic growth of garnet, cordierite and plagioclase. Peak P-T conditions calculated for M-3 are 710 degrees C and 0.60 GPa, preserved in the western part of the EPMIC, west of the unnamed fault.
The schists from the QMMC suffered the early low grade M-1 metamorphism with minimum PT conditions of ca 400 degrees C and 0.35 GPa, comparable to the fine schists (M-1) outcropping to the east. The D-2 deformation is associated with the prograde M-2 metamorphism. The penetrative D-3 stage is related to a medium grade metamorphism M-3, with peak conditions at ca 590 degrees C and 0.55 GPa.
The superimposed stages of deformation and metamorphism reaching high P-T conditions followed by isothermal decompression, defining a clockwise orogenic P-T path. During the Lower Paleozoic, folds were superimposed and recrystallization as well as partial melting at peak conditions occurred. Similar characteristics were described from the basement from other Famatinian-dominated locations of the Sierra de Aconquija and other ranges of the Sierras Pampeanas Orientales.
The imagination of clearly separated core-shell structures is already outdated by the fact, that the nanoparticle core-shell structures remain in terms of efficiency behind their respective bulk material due to intermixing between core and shell dopant ions. In order to optimize the photoluminescence of core-shell UCNP the intermixing should be as small as possible and therefore, key parameters of this process need to be identified. In the present work the Ln(III) ion migration in the host lattices NaYF4 and NaGdF4 was monitored. These investigations have been performed by laser spectroscopy with help of lanthanide resonance energy transfer (LRET) between Eu(III) as donor and Pr(III) or Nd(III) as acceptor. The LRET is evaluated based on the Forster theory. The findings corroborate the literature and point out the migration of ions in the host lattices. Based on the introduced LRET model, the acceptor concentration in the surrounding of one donor depends clearly on the design of the applied core-shell-shell nanoparticles. In general, thinner intermediate insulating shells lead to higher acceptor concentration, stronger quenching of the Eu(III) donor and subsequently stronger sensitization of the Pr(III) or the Nd(III) acceptors. The choice of the host lattice as well as of the synthesis temperature are parameters to be considered for the intermixing process.
Carbon Adsorbents from Spent Coffee for Removal of
Methylene Blue and Methyl Orange from Water
(2021)
Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed.
Carbon adsorbents from spent coffee for removal of methylene blue and methyl orange from water
(2021)
Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed.
Thirteen N-butylpyridinium salts, including three monometallic [C4Py](2)[MCl4], nine bimetallic [C4Py](2)[(M1-xMxCl4)-M-a-Cl-b] and one trimetallic compound [C4Py](2)[(M1-y-zMyMz (c) Cl4)-M-a-M-b] (M=Co, Cu, Mn; x=0.25, 0.50 or 0.75 and y=z=0.33), were synthesized and their structure and thermal and electrochemical properties were studied. All compounds are ionic liquids (ILs) with melting points between 69 and 93 degrees C. X-ray diffraction proves that all ILs are isostructural. The conductivity at room temperature is between 10(-4) and 10(-8) S cm(-1). Some Cu-based ILs reach conductivities of 10(-2) S cm(-1), which is, however, probably due to IL dec. This correlates with the optical bandgap measurements indicating the formation of large bandgap semiconductors. At elevated temperatures approaching the melting points, the conductivities reach up to 1.47x10(-1) S cm(-1) at 70 degrees C. The electrochemical stability windows of the ILs are between 2.5 and 3.0 V.
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.
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.
Garnet of eclogite (formerly termed garnet clinopyroxenite) hosted in lenses of orogenic garnet peridotite from the Granulitgebirge, NW Bohemian Massif, contains unique inclusions of granitic melt, now either glassy or crystallized. Analysed glasses and re‐homogenized inclusions are hydrous, peraluminous, and enriched in highly incompatible elements characteristic of the continental crust such as Cs, Li, B, Pb, Rb, Th, and U. The original melt thus represents a pristine, chemically evolved metasomatic agent, which infiltrated the mantle via deep continental subduction during the Variscan orogeny. The bulk chemical composition of the studied eclogites is similar to that of Fe‐rich basalt and the enrichment in LILE and U suggest a subduction‐related component. All these geochemical features confirm metasomatism. In comparison with many other garnet+clinopyroxene‐bearing lenses in peridotites of the Bohemian Massif, the studied samples from Rubinberg and Klatschmühle are more akin to eclogite than pyroxenites, as reflected in high jadeite content in clinopyroxene, relatively low Mg, Cr, and Ni but relatively high Ti. However, trace elements of both bulk rock and individual mineral phases show also important differences making these samples rather unique. Metasomatism involving a melt requiring a trace element pattern very similar to the composition reported here has been suggested for the source region of rocks of the so‐called durbachite suite, that is, ultrapotassic melanosyenites, which are found throughout the high‐grade Variscan basement. Moreover, the Th, U, Pb, Nb, Ta, and Ti patterns of these newly studied melt inclusions (MI) strongly resemble those observed for peridotite and its enclosed pyroxenite from the T‐7 borehole (Staré, České Středhoři Mountains) in N Bohemia. This suggests that a similar kind of crustal‐derived melt also occurred here. This study of granitic MI in eclogites from peridotites has provided the first direct characterization of a preserved metasomatic melt, possibly responsible for the metasomatism of several parts of the mantle in the Variscides.
Britholite group minerals (REE,Ca)(5)[(Si,P)O-4](3)(OH,F) are widespread rare-earth minerals in alkaline rocks and their associated metasomatic zones, where they usually are minor accessory phases. An exception is the REE deposit Rodeo de los Molles, Central Argentina, where fluorbritholite-(Ce) (FBri) is the main carrier of REE and is closely intergrown with fluorapatite (FAp). These minerals reach an abundance of locally up to 75 modal% (FBri) and 20 modal% (FAp) in the vein mineralizations. The Rodeo de los Molles deposit is hosted by a fenitized monzogranite of the Middle Devonian Las Chacras-Potrerillos batholith. The REE mineralization consists of fluorbritholite-(Ce), britholite-(Ce), fluorapatite, allanite-(Ce), and REE fluorcarbonates, and is associated with hydrothermal fluorite, quartz, albite, zircon, and titanite. The REE assemblage takes two forms: irregular patchy shaped REE-rich composites and discrete cross-cutting veins. The irregular composites are more common, but here fluorbritholite-(Ce) is mostly replaced by REE carbonates. The vein mineralization has more abundant and better-preserved britholite phases. The majority of britholite grains at Rodeo de los Molles are hydrothermally altered, and alteration is strongly enhanced by metamictization, which is indicated by darkening of the mineral, loss of birefringence, porosity, and volume changes leading to polygonal cracks in and around altered grains. A detailed electron microprobe study of apatite-britholite minerals from Rodeo de los Molles revealed compositional variations in fluorapatite and fluorbritholite-(Ce) consistent with the coupled substitution of REE3+ + Si4+ = Ca2+ + P5+ and a compositional gap of similar to 4 apfu between the two phases, which we interpret as a miscibility gap. Micrometer-scale intergrowths of fluorapatite in fluorbritholite-(Ce) minerals and vice versa are chemically characterized here for the first time and interpreted as exsolution textures that formed during cooling below the proposed solvus.
By varying reaction parameters for the syntheses of the hydrogen-bonded metal-imidazolate frameworks (HIF) HIF-1 and HIF-2 (featuring 14 Zn and 14 Co atoms, respectively) to increase their yields and crystallinity, we found that HIF-1 is generated in two different frameworks, named as HIF-1a and HIF-1b. HIF-1b is isostructural to HIF-2. We determined the gas sorption and magnetic properties of HIF-2. In comparison to HIF-1a (Brunauer-Emmett-Teller (BET) surface area of 471m(2) g(-1)), HIF-2 possesses overall very low gas sorption uptake capacities [BET(CO2) surface area=85m(2) g(-1)]. Variable temperature magnetic susceptibility measurement of HIF-2 showed antiferromagnetic exchange interactions between the cobalt(II) high-spin centres at lower temperature. Theoretical analysis by density functional theory confirmed this finding. The UV/Vis-reflection spectra of HIF-1 (mixture of HIF-1a and b), HIF-2 and HIF-3 (with 14 Cd atoms) were measured and showed a characteristic absorption band centered at 340nm, which was indicative for differences in the imidazolate framework.
Garnet of eclogite (formerly termed garnet clinopyroxenite) hosted in lenses of orogenic garnet peridotite from the Granulitgebirge, NW Bohemian Massif, contains unique inclusions of granitic melt, now either glassy or crystallized. Analysed glasses and re‐homogenized inclusions are hydrous, peraluminous, and enriched in highly incompatible elements characteristic of the continental crust such as Cs, Li, B, Pb, Rb, Th, and U. The original melt thus represents a pristine, chemically evolved metasomatic agent, which infiltrated the mantle via deep continental subduction during the Variscan orogeny. The bulk chemical composition of the studied eclogites is similar to that of Fe‐rich basalt and the enrichment in LILE and U suggest a subduction‐related component. All these geochemical features confirm metasomatism. In comparison with many other garnet+clinopyroxene‐bearing lenses in peridotites of the Bohemian Massif, the studied samples from Rubinberg and Klatschmühle are more akin to eclogite than pyroxenites, as reflected in high jadeite content in clinopyroxene, relatively low Mg, Cr, and Ni but relatively high Ti. However, trace elements of both bulk rock and individual mineral phases show also important differences making these samples rather unique. Metasomatism involving a melt requiring a trace element pattern very similar to the composition reported here has been suggested for the source region of rocks of the so‐called durbachite suite, that is, ultrapotassic melanosyenites, which are found throughout the high‐grade Variscan basement. Moreover, the Th, U, Pb, Nb, Ta, and Ti patterns of these newly studied melt inclusions (MI) strongly resemble those observed for peridotite and its enclosed pyroxenite from the T‐7 borehole (Staré, České Středhoři Mountains) in N Bohemia. This suggests that a similar kind of crustal‐derived melt also occurred here. This study of granitic MI in eclogites from peridotites has provided the first direct characterization of a preserved metasomatic melt, possibly responsible for the metasomatism of several parts of the mantle in the Variscides.