Photocatalytic oxidation of propene in gas phase at low concentration by optimized TiO2 nanoparticles

In the present study, nanocrystalline titanium dioxide (TiO2) was prepared by sol–gel method at low temperature from titanium tetraisopropoxide (TTIP) and characterized by different techniques (gas adsorption, XRD, TEM and FTIR). Variables of the synthesis, such as the hydrolyzing agent (acetic acid or isopropanol) and calcination temperatures (300–800 °C), were analyzed to get uniform size TiO2 nanoparticles. The effect that these two variables have on the structure of the resultant TiO2 nanoparticles and on their photocatalytic activity is investigated. The photocatalytic activities of TiO2 nanoparticles were evaluated for propene oxidation at low concentration (100 ppmv) under two different kinds of UV light (UV-A ∼ 365 nm and UV-C ∼ 257.7 nm) and compared with Degussa TiO2 P-25, used as reference sample. The results show that both hydrolyzing agents allow to prepare TiO2 nanoparticles and that the hydrolyzing agent influences the crystalline structure and its change with the thermal treatments. Interestingly, the prepared TiO2 nanoparticles possess anatase phase with small crystalline size, high surface area and higher photocatalytic activity for propene oxidation than commercial TiO2 (Degussa P-25) under UV-light. Curiously, these prepared TiO2 nanoparticles are more active with the 365 nm source than with the 257.7 nm UV-light, which is a remarkable advantage from an application point of view. Additionally, the obtained results are particularly good when acetic acid is the hydrolyzing agent at both wavelengths used, possibly due to the high crystallinity, low anatase phase size and high surface oxygen groups’ content in the nanoparticles prepared with it, in comparison to those prepared using isopropanol.

Planktonic foraminifer abundance and estimated sea surface temperatures and salinities of DSDP Leg 74 holes

Two hydraulic piston cores containing the total Quaternary suite were analyzed quantitatively in their planktonic foraminiferal contents. For the Early Pleistocene, the Caribbean standard zonation (BOLLI & PREMOLI-SILVA) can be adopted and refined by the introduction of an additional subzone at its base (the Globorotalia triangula subzone). Local substages are proposed for the Late Pleistocene because index fossils are missing. The use of the transfer-function technique resulted in paleotemperature and paleosalinity curves with a time resolution of cycles of about 4-68,000 years duration. The Early Pleistocene paleoenvironment is characterized by low oscillations of the surface water temperatures, followed by a distinct cooling trend during the Globorotalia viola subzone, a period of smoothed cycles during the Globorotalia hessi subzone and distinctly developed cycles during the late Pleistocene since the oxygen isotope termination III. Grainsize distribution and several dissolution indices gave evidence for current activities on the top of the Walvis Ridge, where the amount of fine grained components in the sediment is reduced in comparison with that of the flanks.

Aragonite content, stable oxygen isotopes of Globigerioides ruber, and age of ODP Site 166-1006 sediments

The 1.4-m.y.-long stable oxygen isotope record of Site 1006 in the low-latitude North Atlantic Ocean shows large glacial/interglacial amplitude changes caused by a combination of temperature and salinity fluctuations. A trend of increased sea-surface temperatures during the interglacial periods is present in the record beginning at isotopic Stage 11 and ultimately leading to the lightest d18O values in isotopic Stages 9, 5, and 1. Maximum d18O values are recorded during glacial isotopic Stages 6 and 8. Stable isotopic variability increased during the Brunhes Chron at the 100-ka time scale. The large amplitude changes can best be explained by global and regional ocean circulation changes. Increased strengthened return flow of warm salty water from the Pacific may have occurred during interglacial periods since isotopic Stage 11, which was largely reduced during glacial periods. The large climate fluctuations had a profound effect on the shallow-water carbonate production of the Great Bahama Bank. The aragonite content of the sediments shows fluctuations that follow the d18O record. The leeward side of the Great Bahama Bank received increased input of platform material during sea-level highstands when the sea-surface waters were warm.

Stable carbon and oxygen isotope ratios of late Eocene and Oligocene foraminifera from the Atlantic Ocean

Oxygen isotope analyses of late Eocene and Oligocene planktonic foraminifers from low and middle latitude sites in the Atlantic Basin show that different species from the same samples can yield significantly different isotopic values. The range of isotopic values observed between species is greatest at low-latitudes and declines poleward. Many planktonic foraminifers exhibit a systematic isotopic ranking with respect to each other and can therefore be grouped on the basis of their isotopic ranking. The isotopic ranking of some taxa, however, appears to vary geographically and/or through time. Isotopic and paleontologic data from DSDP Site 522 indicate that commonly used isotopic temperature scales underestimate Oligocene sea surface temperatures. We suggest these temperature scales require revision to reflect the presence of Oligocene glaciation. Comparison of isotopic and paleontologic data from Sites 522, 511 and 277 suggests cold, low-salinity surface waters were present in high southern latitudes during the early Oligocene. Lowsalinity, high latitude surface waters could be caused by Eocene/Oligocene paleogeography or by the production of warm saline bottom water.

Benthic oxygen isotope and dust flux record from ODP Site 108-659 in the North Atlantic

High-resolution benthic oxygen isotope and dust flux records from Ocean Drilling Program site 659 have been analyzed to extend the astronomically calibrated isotope timescale for the Atlantic from 2.85 Ma back to 5 Ma. Spectral analysis of the delta18O record indicates that the 41-kyr period of Earth's orbital obliquity dominates the Pliocene record. This is shown to be true regardless of fundamental changes in the Earth's climate during the Pliocene. However, the cycles of Sahelian aridity fluctuations indicate a shift in spectral character near 3 Ma. From the early Pliocene to 3 Ma, the periodicities were dominantly precessional (19 and 23 kyr) and remained strong until 1.5 Ma. Subsequent to 3 Ma, the variance at the obliquity period (41 kyr) increased. The timescale tuned to precession suggests that the Pliocene was longer than previously estimated by more than 0.5 m.y. The tuned ages for the magnetic boundaries Gauss/Gilbert and Top Cochiti are about 6-8% older than the ages of the conventional timescale. A major phase of Pliocene northern hemisphere ice growth occurred between 3.15 Ma and 2.5 Ma. This was marked by a gradual increase in glacial Atlantic delta18O values of 1per mil and an increase in amplitude variations by up to 1.5 per mil, much larger than in the Pacific deepwater record (site 846). The first maxima occured in cold stages G6-96 between 2.7 Ma and 2.45 Ma. Prior to 3 Ma, the isotope record is characterized by predominantly low amplitude fluctuations (< 0.7 per mil). When obliquity forcing was at its minimum between 4.15 and 3.6 Ma and during the Kaena interval, delta18O amplitude fluctuations were minimal. From 4.9 to 4.3 Ma, the delta18O values decreased by about 0.5 per mil, reaching a long-term minimum at 4.15 Ma, suggesting higher deepwater temperatures or a deglaciation. Deepwater cooling and/or an increase in ice volume is indicated by a series of short-term delta18O fluctuations between 3.8 and 3.6 Ma.

Stable oxygen, hydrogene and chlorine isotopes of mid-Atlantic abyssal peridotites

Serpentinized abyssal peridotites sampled by the Ocean Drilling Program Leg 209 along the mid-Atlantic Ridge near the 15°20'N Fracture Zone have been analyzed for oxygen, hydrogen, and chlorine isotope compositions in order to determine isotopic behavior under a wide range of serpentinization conditions and place constraints on fluid history. Oxygen and hydrogen thermometry suggests peak serpentinization temperatures of 300-500°C. Serpentine separates have low deltaD values possibly due to a magmatic fluid component or low-temperature exchange during seafloor weathering. Chlorine geochemistry focused on three holes: 1274A and 1272A (serpentinized peridotites) and 1268A (serpentinite locally altered to talc). Concentrations of both, water-soluble chloride (WSC) and structurally bound chloride (SBC) are significantly lower at Hole 1268A compared to Holes 1274A and 1272A. The delta37Cl values for WSC and SBC of serpentinites in Holes 1274A and 1272A are slightly positive (avg. WSC = 0.20 per mil, n = 22 and avg. SBC = 0.35 per mil, n = 22), representing typical seawater-hydration conditions commonly determined for abyssal peridotite. The SBC of serpentinites from Hole 1268A are also positive (avg. = 0.63 per mil); whereas, the SBC in talc-dominated samples is negative (avg. = -1.22 per mil). The WSC of both talc- and serpentine-dominated samples are also negative (avg. = -0.15 per mil). We interpret the chlorine isotope data to preserve a record of multiple fluid events. As seawater hydrated the peridotite, 37Cl was preferentially incorporated into the forming serpentine and water-soluble salts, yielding similar delta37Cl values on a regional scale as sampled by Holes 1268A, 1274A and 1272A. The resultant pore fluid was left depleted in 37Cl. Locally (Hole 1268A), this evolved fluid was remobilized possibly due to the initiation of hydrothermal circulation in response to emplacement of a mafic magma body. The low delta37Cl pore fluids attained elevated SiO2 and sulfur concentrations due to interaction with the gabbroic intrusion and, when ascending through the surrounding serpentinite, caused formation of isotopically negative talc. This secondary fluid also flushed the preserved serpentinite of its previously formed salts, resulting in negative delta37Cl WSC values. The delta37Cl SBC values of the serpentinite samples remained unmodified by reaction with the secondary fluid.

Oxygen isotope and paleomagnetic stratigraphy of sediment core V28-239

Core Vema 28-238 preserves an excellent oxygen isotope and magnetic stratigraphy and is shown to contain undisturbed sediments deposited continuously through the past 870,000 yr. Detailed correlation with sequences described by Emiliani in the Caribbean and Atlantic Ocean is demonstrated. The boundaries of 22 stages representing alternating times of high and low Northern Hemisphere ice volume are recognized and dated. The record is interpreted in terms of Northern Hemisphere ice accumulation, and is used to estimate the range of temperature variation in the Caribbean.

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"Metallurgy and Ceramics."

Petrology and geochemistry of early cretaceous bimodal continental flood volcanism of the NW Etendeka, Namibia. Part 2: Characteristics and petrogenesis of the high-Ti latite and high-Ti and low-Ti voluminous quartz latite eruptives

As a result of their relative concentration towards the respective Atlantic margins, the silicic eruptives of the Parana (Brazil)-Etendeka large igneous province are disproportionately abundant in the Etendeka of Namibia. The NW Etendeka silicic units, dated at similar to132 Ma, occupy the upper stratigraphic levels of the volcanic sequences, restricted to the coastal zone, and comprise three latites and five quartz latites (QL). The large-volume Fria QL is the only low-Ti type. Its trace element and isotopic signatures indicate massive crustal input. The remaining NW Etendeka silicic units are enigmatic high-Ti types, geochemically different from low-Ti types. They exhibit chemical affinities with the temporally overlapping Khumib high-Ti basalt (see Ewart et al. Part 1) and high crystallization temperatures (greater than or equal to980 to 1120degreesC) inferred from augite and pigeonite phenocrysts, both consistent with their evolution from a mafic source. Geochemically, the high-Ti units define three groups, thought genetically related. We test whether these represent independent liquid lines of descent from a common high-Ti mafic parent. Although the recognition of latites reduces the apparent silica gap, difficulty is encountered in fractional crystallization models by the large volumes of two QL units. Numerical modelling does, however, support large-scale open-system fractional crystallization, assimilation of silicic to basaltic materials, and magma mixing, but cannot entirely exclude partial melting processes within the temporally active extensional environment. The fractional crystallization and mixing signatures add to the complexity of these enigmatic and controversial silicic magmas. The existence, however, of temporally and spatially overlapping high-Ti basalts is, in our view, not coincidental and the high-Ti character of the silicic magmas ultimately reflects a mantle signature.