Insights into the Active Species of Nanoparticle-Functionalized Hierarchical Zeolites in Alkylation Reactions

Supported iron oxide nanoparticles have been incorporated onto hierarchical zeolites by microwave-assisted impregnation and mechanochemical grinding. Nanoparticle-functionalised porous zeolites were characterised by a number of analytical techniques such as XRD, N2 physisorption, TEM, and surface acidity measurements. The catalytic activities of the synthesised nanomaterials were investigated in an alkylation reaction. The results pointed to different species with varying acidity and accessibility in the materials, which provided essentially different catalytic activities in the alkylation of toluene with benzyl chloride under microwave irradiation, selected as the test reaction.

Geochemistry of basalts from ODP Leg 49, North Atlantic Ocean

The geochemistry of basalts recovered from seven sites in the North Atlantic is described with particular reference to minor elements. Three sites (407, 408, and 409) along the same mantle flow line, transverse to the Reykjanes Ridge at about 63°N, provide information on the composition of basalts erupted over a 34-m.y. interval between 2.3 and 36 m.y. ago. At Site 410, at 45°N, penetration into 10 m.y.-old crust west of the ridge axis permits comparisons with young basalts dredged from the median valley at 45°N. Three sites in the FAMOUS area at about 36°N provided material from very young (1 m.y.) basaltic crust (Site 411), and material to test the geochemical coherence of basalts of different ages (1.5 and 3.5 m.y.) on either side of a fracture zone (Sites 412 and 413). These sites complement earlier data from dredged and drilled sites (Leg 37) in the FAMOUS area. At Site 407, four geochemically distinct basalt units occur, with different normative and rare-earth element (REE) characteristics, and there is a clear correlation with magnetic stratigraphy. Yet there is a remarkable consistency in incompatible element ratios between these units, indicating derivation from an essentially similar mantle source. The basalts from the younger sites, 408 and 409, show a similar range of normative and REE variation, but incompatible element ratios are identical to those at Site 407, indicating that basalts at all three sites were produced from a mantle source which was geochemically relatively uniform. Rare-earth differences between the basalts can be interpreted in terms of variations in the degree and depth of partial melting causing HREE (+Y) retention in the source, although there may be some inter-site differences with respect to REE. A similar picture is presented at 45°N. Apparently a range of tholeiitic, transitional, and alkalic basalts were being erupted 10 m.y. ago, which have almost identical geochemical characteristics to those recently erupted in the median valley at 45°N. Incompatible element ratios are markedly different from those recorded at the Reykjanes Ridge. Basalts recovered from the FAMOUS sites are geochemically similar to previous samples recovered from the FAMOUS area, and their incompatible element ratios are similar, but not identical, to those at 45°N. However, total trace element levels are consistently lower than in 45°N basalts, which might imply smaller degrees of partial melting and/or greater depths of magma generation at 45°N, or higher trace element levels in the mantle source at 45°N. Few of the basalts recovered on Leg 49 have the geochemical characteristics of typical "MORB" (e.g., Nazca Plate, Leg 34). The data strongly support models invoking geochemical inhomogeneity in the source regions of basalts produced at the Mid-Atlantic Ridge. However, the data also introduce an additional time factor into such models and demonstrate the uniformity of the mantle source at a particular ridge sector (over periods in excess of 30 m.y.), while emphasizing the marked differences along the ridge. Mixing models invoking "depleted" and "enriched" mantle sources would seem to be inadequate to account for the observed variations.

(Table 4) Chemistry of iron-rich basalts from ODP Hole 106-648B

Analysis numbers 344-370, SAMF 12.5-12.7; 442-369, SAMF 12.7-12.9; 422-77, SAMF 12.9-13.1; 95-156, SAMF 13.1-13.3; 272-82, SAMF 13.3-13.5; 285-33, SAMF 13.5-13.7. Analyses are listed in depth order within each SAMF division.

Sedimentology and geochemistry of ODP Site 184-1144

We analyzed sediment from Ocean Drilling Program (ODP) Site 1144 in the northern South China Sea to examine the weathering response of SE Asia to the strengthening of the East Asian Monsoon (EAM) since 14 ka. Our high-resolution record highlights the decoupling between continental chemical weathering, physical erosion and summer monsoon intensity. Mass accumulation rates, Ti/Ca, K/Rb, hematite/goethite and 87Sr/86Sr show sharp excursions from 11 to 8 ka, peaking at 10 ka. Clay minerals show a shorter-lived response with a higher kaolinite/(illite + chlorite) ratio at 10.7-9.5 ka. However, not all proxies show a clear response to environmental changes. Magnetic susceptibility rises sharply between 12 and 11 ka. Grain-size becomes finer from 14 to 10 ka and then coarsens until ~7 ka, but is probably controlled by bottom current flow and sealevel. Sr and Nd isotopes show that material is dominantly eroded from Taiwan with a lesser flux from Luzon, while clay mineralogy suggests that the primary sources during the Early Holocene were reworked via the shelf in the Taiwan Strait, rather than directly from Taiwan. Erosion was enhanced during monsoon strengthening and caused reworking of chemically weathered Pleistocene sediment largely from the now flooded Taiwan Strait, which was transgressed by ~8 ka, cutting off supply to the deep-water slope. None of the proxies shows an erosional response lasting until ~6 ka, when speleothem oxygen isotope records indicate the start of monsoon weakening. Although more weathered sediments were deposited from 11 to 8 ka when the monsoon was strong these are reworked and represent more weathering during the last glacial maximum (LGM) when the summer monsoon was weaker but the shelves were exposed.

(Table 1, page 168) Iron, manganese, and phosphorus concentrations in Fe-Mn-concretions from the Gulf of Bothnia, northern Baltic Sea

Fe-Mn-concretions of a spheroidal type were found according to electron probe determinations to consist of alternating iron- and manganese-rich layers. This pattern was ascribed to seasonal variations in the physico-chemical conditions governing the precipitation of the hydrous oxides of iron and manganese. Calculations based on the rhythmic growth of the concretions investigated gave a mean accumulation rate of 0.15-0.20 mm/yr. The rather high phosphorus content (average 3.5 % P2O5) of the concretions was found to be concentrated in the iron-rich layers, probably as a result of the scavenging effect of ferric hydroxide.

Geochemistry at DSDP Sites 69-505, 69-504 and 70-504

Deep basement penetration during Legs 69 and 70 at Hole 504B in the Panama Basin allowed the recovery of a 561.5-meter sequence of basaltic pillows, thin flows, and breccias interspersed with thick massive flows. The lavas, which are aphyric to moderately plagioclase-olivine-clinopyroxene phyric, are petrologically indistinguishable from typical mid-ocean-ridge basalts (MORB). Some units are distinctive in that they carry accessory chrome-spinel microphenocrysts or emerald green clinopyroxene phenocrysts. Major and trace element analyses were carried out on 67 samples using X-ray fluorescence techniques. The basalts resemble normal MORB in terms of major elements. However, the trace element analyses show that most of the basalts are characterized by very strong depletion in the more incompatible elements compared with, for instance, normal (N type) MORB from the Atlantic at 22°N. Interdigitated with these units are one or two units that have distinctly higher incompatible element concentrations similar to those in basalts of the transitional (T) type from the Reykjanes Ridge (63°N in the Mid-Atlantic Ridge). All the basalts appear to have undergone some high-level crystal fractionation, although this has not proceeded to the extent of yielding ferrobasalts as it has at the adjacent Galapagos Spreading Center or along the East Pacific Rise. The magnetic anomalies are of lower amplitude than in the latter two regions, which suggests that the absence of ferrobasalts may be a general feature of the ocean crust generated at the Costa Rica Rift. The presence of two distinct magma types, one strongly depleted and the other moderately enriched in incompatible elements, suggests that magma chambers at the spreading center are discontinuous rather than continuous and that there is some chemical heterogeneity in the underlying mantle source. Observed variations in incompatible element ratios of basalts from the more depleted group could, however, reflect mixing between these two magma types. In general it would appear that the mantle feeding the Costa Rica Rift is significantly more depleted in incompatible trace elements than that feeding the Mid-Atlantic Ridge.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

Natural remanent magnetization of IODP Expedition 308, Holes U1319A, U1320A, U1322B, and U1324B from the northern Gulf of Mexico

Paleomagnetic analyses of the natural remanent magnetization of >1700 vertically oriented sediment samples from Integrated Ocean Drilling Program (IODP) Holes U1319A, U1320A, U1322B, and U1324B in the northern Gulf of Mexico reveal complex magnetostratographic signals for the Brazos-Trinity and Ursa region carried by detrital iron oxide minerals. Additionally, gyroremanent magnetization was observed to form during alternating-field demagnetization of samples containing an enhanced amount of magnetic iron sulfide minerals. Most characteristic remanent magnetization inclinations are reasonable for the site latitudes. Stable declinations allow for azimuth correction of the formerly unoriented drill cores.

Major and trace element composition in the Central Indian Ocean Basin ferrobasalts (Table 2, 3)

We report the occurrence of ferrobasalts recovered from the Central Indian Ocean Basin crust generated at the Southeast Indian Ridge during a phase of moderate to fast spreading accretion (~110-190 mm/yr, full rate).The rocks are rich in plagioclase, FeO* (13/19 %), and TiO2 (2.27/2.76 %), poor in olivine and MgO (3.44/6.20%), and associated with topographic highs and increased amplitude magnetic anomalies corresponding to chrons A25 and A24. We suggest that secon dary eruptions from ancient N-MORB magma, which may have been trapped at a shallow depth in a horizon of neutral buoyancy, could have produced the ferrobasalts.

Sedimentology, geochemistry and paleomagnetic of ODP Hole 151-913B

The Eocene and Oligocene epochs (55 to 23 million years ago) comprise a critical phase in Earth history. An array of geological records (Zachos et al., 2001, doi:10.1126/science.1059412; Lear et al., 2000, doi:10.1126/science.287.5451.269; Coxall et al., 2005, doi:10.1038/nature03135; Pekar et al., 2005; doi:10.1130/B25486.1; Strand et al., 2003, doi:10.1016/S0031-0182(03)00396-1) supported by climate modelling (DeConto and Pollard, 2003, doi:10.1038/nature01290) indicates a profound shift in global climate during this interval, from a state that was largely free of polar ice caps to one in which ice sheets on Antarctica approached their modern size. However, the early glaciation history of the Northern Hemisphere is a subject of controversy (Coxall et al., 2005, doi:10.1038/nature03135; Tripati et al., 2005, doi:10.1038/nature03874; Wolf-Welling et al., 1996, doi:10.2973/odp.proc.sr.151.139.1996; Moran et al., 2006, doi:10.1038/nature04800). Here we report stratigraphically extensive ice-rafted debris, including macroscopic dropstones, in late Eocene to early Oligocene sediments from the Norwegian-Greenland Sea that were deposited between about 38 and 30 million years ago. Our data indicate sediment rafting by glacial ice, rather than sea ice, and point to East Greenland as the likely source. Records of this type from one site alone cannot be used to determine the extent of ice involved. However, our data suggest the existence of (at least) isolated glaciers on Greenland about 20 million years earlier than previously documented (Winkler et al., 2002, doi:10.1007/s005310100199), at a time when temperatures and atmospheric carbon dioxide concentrations were substantially higher.

Geochemistry and Fe/(Ti + Ti), x, Curie temperature, and oxidation parameter z at DSDP Hole 597C

Electron microprobe and thermomagnetic analyses of selected basalt samples from Hole 597C were performed. The main purpose of this work was to investigate and estimate the degree of oxidation of the samples using the ratios of Fe to Ti and the Curie temperatures obtained from thermomagnetic curves. The results show that the magnetic properties of samples from Hole 597C change at a sub-bottom depth of 100 m, and that low-temperature and high-temperature oxidation processes prevailed above and below 100 m, respectively.