Surface Ocean CO2 Atlas (SOCAT) V1.4

A well-documented, publicly available, global data set of surface ocean carbon dioxide (CO2) parameters has been called for by international groups for nearly two decades. The Surface Ocean CO2 Atlas (SOCAT) project was initiated by the international marine carbon science community in 2007 with the aim of providing a comprehensive, publicly available, regularly updated, global data set of marine surface CO2, which had been subject to quality control (QC). Many additional CO2 data, not yet made public via the Carbon Dioxide Information Analysis Center (CDIAC), were retrieved from data originators, public websites and other data centres. All data were put in a uniform format following a strict protocol. Quality control was carried out according to clearly defined criteria. Regional specialists performed the quality control, using state-of-the-art web-based tools, specially developed for accomplishing this global team effort. SOCAT version 1.5 was made public in September 2011 and holds 6.3 million quality controlled surface CO2 data points from the global oceans and coastal seas, spanning four decades (1968-2007). Three types of data products are available: individual cruise files, a merged complete data set and gridded products. With the rapid expansion of marine CO2 data collection and the importance of quantifying net global oceanic CO2 uptake and its changes, sustained data synthesis and data access are priorities.

Nanostructured copper oxides and phosphates from a new solid-state route

Nanostructured copper containing materials of CuO, Cu3(PO4)3 and Cu2P2O7 have been prepared by solid-state pyrolysis of molecular CuCl2·NC5H4OH (I), CuCl2·CNCH2C6H4OH (II), oligomeric [Cu(PPh3)Cl]4 (III), N3P3[OC6H4CH2CN·CuCl]6[PF6] (IV), N3P3[OC6H5]5[OC5H4N·Cu][PF6] (V), polymeric chitosan·(CuCl2)n (VI) and polystyrene-co-4-vinylpyridine PS-b-4-PVP·(CuCl2) (VII) precursors. The products strongly depend on the precursor used. The pyrolytic products from phosphorus-containing precursors (III), (IV) and (V) are Cu phosphates or pyrophosphates, while non-phosphorous-containing precursors (VI) and (VII), result in mainly CuO. The use of chitosan as a solid-state template/stabilizer induces the formation of CuO and Cu2O nanoparticles. Copper pyrophosphate (Cu2P2O7) deposited on Si using (IV) as the precursor exhibits single-crystal dots of average diameter 100 nm and heights equivalent to twice the unit cell b-axis (1.5–1.7 nm) and an areal density of 5.1–7.7 Gigadots/in.2. Cu2P2O7 deposited from precursor (VI) exhibits unique labyrinthine high surface area deposits. The morphology of CuO deposited on Si from pyrolysis of (VI) depends on the polymer/Cu meta ratio. Magnetic measurements performed using SQUID on CuO nanoparticle networks suggest superparamagnetic behavior. The results give insights into compositional, shape and morphological control of the as-formed nanostructures through the structure of the precursors.

Single-crystal micro/nanostructures and thin films of lamellar molybdenum oxide by solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene

The solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene is demonstrated to be a new, simple and versatile solid-state templating method for obtaining single-crystal micro- and nanocrystals of transition and valve metal oxides. The technique, when applied to Mo-containing organometallics N3P3[OC6H4CH2CN·Mo(CO)5]6 and N3P3[OC6H4CH2CN·Mo(CO)4 py]6, results in stand-alone and surface-deposited lamellar MoO3 single crystals, as determined by electron and atomic force microscopies and X-ray diffraction. The size and morphology of the resulting crystals can be tuned by the composition of the precursor. X-ray photoelectron and infrared spectroscopies indicate that the deposition of highly lamellar MoO3 directly on an oxidized (400 nm SiO2) surface or (100) single-crystal silicon surfaces yields a layered uniphasic single-crystal film formed by cluster diffusion on the surface during pyrolysis of the metal-carbonyl derivatives. For MoO3 in its layered form, this provides a new route to an important intercalation material for high energy density battery materials.

Synthesis and characterization of cyclotriphosphazenes containing silicon as single solid-state precursors for the formation of silicon/phosphorus nanostructured materials

The synthesis and characterization of new organosilicon derivatives of N3P3Cl6, N3P3[NH(CH2)3Si(OEt)3]6 (1), N3P3[NH(CH2)3Si(OEt)3]3[NCH3(CH2)3CN]3 (2), and N3P3[NH(CH2)3Si(OEt)3]3[HOC6H4(CH2)CN]3 (3) are reported. Pyrolysis of 1, 2, and 3 in air and at several temperatures results in nanostructured materials whose composition and morphology depend on the temperature of pyrolysis and the substituents of the phosphazenes ring. The products stem from the reaction of SiO2 with P2O5, leading to either crystalline Si5(PO4)6O, SiP2O7 or an amorphous phase as the glass Si5(PO4)6O/3SiO2·2P2O5, depending on the temperature and nature of the trimer precursors. From 1 at 800 °C, core−shell microspheres of SiO2 coated with Si5(PO4)6O are obtained, while in other cases, mesoporous or dense structures are observed. Atomic force microscopy examination after deposition of the materials on monocrystalline silicon wafers evidences morphology strongly dependent on the precursors. Isolated islands of size ∼9 nm are observed from 1, whereas dense nanostructures with a mean height of 13 nm are formed from 3. Brunauer−Emmett−Teller measurements show mesoporous materials with low surface areas. The proposed growth mechanism involves the formation of cross-linking structures and of vacancies by carbonization of the organic matter, where the silicon compounds nucleate. Thus, for the first time, unique silicon nanostructured materials are obtained from cyclic phosphazenes containing silicon.

Effects of alternating current voltage amplitude and oxide capacitance on mid-gap interface state defect density extractions in In0.53Ga 0.47As capacitors

This work looks at the effect on mid-gap interface state defect density estimates for In0.53Ga0.47As semiconductor capacitors when different AC voltage amplitudes are selected for a fixed voltage bias step size (100 mV) during room temperature only electrical characterization. Results are presented for Au/Ni/Al2O3/In0.53Ga0.47As/InP metal–oxide–semiconductor capacitors with (1) n-type and p-type semiconductors, (2) different Al2O3 thicknesses, (3) different In0.53Ga0.47As surface passivation concentrations of ammonium sulphide, and (4) different transfer times to the atomic layer deposition chamber after passivation treatment on the semiconductor surface—thereby demonstrating a cross-section of device characteristics. The authors set out to determine the importance of the AC voltage amplitude selection on the interface state defect density extractions and whether this selection has a combined effect with the oxide capacitance. These capacitors are prototypical of the type of gate oxide material stacks that could form equivalent metal–oxide–semiconductor field-effect transistors beyond the 32 nm technology node. The authors do not attempt to achieve the best scaled equivalent oxide thickness in this work, as our focus is on accurately extracting device properties that will allow the investigation and reduction of interface state defect densities at the high-k/III–V semiconductor interface. The operating voltage for future devices will be reduced, potentially leading to an associated reduction in the AC voltage amplitude, which will force a decrease in the signal-to-noise ratio of electrical responses and could therefore result in less accurate impedance measurements. A concern thus arises regarding the accuracy of the electrical property extractions using such impedance measurements for future devices, particularly in relation to the mid-gap interface state defect density estimated from the conductance method and from the combined high–low frequency capacitance–voltage method. The authors apply a fixed voltage step of 100 mV for all voltage sweep measurements at each AC frequency. Each of these measurements is repeated 15 times for the equidistant AC voltage amplitudes between 10 mV and 150 mV. This provides the desired AC voltage amplitude to step size ratios from 1:10 to 3:2. Our results indicate that, although the selection of the oxide capacitance is important both to the success and accuracy of the extraction method, the mid-gap interface state defect density extractions are not overly sensitive to the AC voltage amplitude employed regardless of what oxide capacitance is used in the extractions, particularly in the range from 50% below the voltage sweep step size to 50% above it. Therefore, the use of larger AC voltage amplitudes in this range to achieve a better signal-to-noise ratio during impedance measurements for future low operating voltage devices will not distort the extracted interface state defect density.

Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius

In this paper, we use density functional theory corrected for on-site Coulomb interactions (DFT + U) and hybrid DFT (HSE06 functional) to study the defects formed when the ceria (110) surface is doped with a series of trivalent dopants, namely, Al3+, Sc3+, Y3+, and In 3+. Using the hybrid DFT HSE06 exchange-correlation functional as a benchmark, we show that doping the (110) surface with a single trivalent ion leads to formation of a localized MCe / + O O • (M = the 3+ dopant), O- hole state, confirming the description found with DFT + U. We use DFT + U to investigate the energetics of dopant compensation through formation of the 2MCe ′ +VO ̈ defect, that is, compensation of two dopants with an oxygen vacancy. In conjunction with earlier work on La-doped CeO2, we find that the stability of the compensating anion vacancy depends on the dopant ionic radius. For Al3+, which has the smallest ionic radius, and Sc3+ and In3+, with intermediate ionic radii, formation of a compensating oxygen vacancy is stable. On the other hand, the Y3+ dopant, with an ionic radius close to that of Ce4+, shows a positive anion vacancy formation energy, as does La3+, which is larger than Ce4+ (J. Phys.: Condens. Matter 2010, 20, 135004). When considering the resulting electronic structure, in Al3+ doping, oxygen hole compensation is found. However, Sc 3+, In3+, and Y3+ show the formation of a reduced Ce3+ cation and an uncompensated oxygen hole, similar to La3+. These results suggest that the ionic radius of trivalent dopants strongly influences the final defect formed when doping ceria with 3+ cations. In light of these findings, experimental investigations of these systems will be welcome.

Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.

Micro-Fabricated Surface Trap and Cavity Integration for Trapped Ion Quantum Computing

Atomic ions trapped in micro-fabricated surface traps can be utilized as a physical platform with which to build a quantum computer. They possess many of the desirable qualities of such a device, including high fidelity state preparation and readout, universal logic gates, long coherence times, and can be readily entangled with each other through photonic interconnects. The use of optical cavities integrated with trapped ion qubits as a photonic interface presents the possibility for order of magnitude improvements in performance in several key areas of their use in quantum computation. The first part of this thesis describes the design and fabrication of a novel surface trap for integration with an optical cavity. The trap is custom made on a highly reflective mirror surface and includes the capability of moving the ion trap location along all three trap axes with nanometer scale precision. The second part of this thesis demonstrates the suitability of small micro-cavities formed from laser ablated fused silica substrates with radii of curvature in the 300-500 micron range for use with the mirror trap as part of an integrated ion trap cavity system. Quantum computing applications for such a system include dramatic improvements in the photonic entanglement rate up to 10 kHz, the qubit measurement time down to 1 microsecond, and the measurement error rates down to the 10e-5 range. The final part of this thesis details a performance simulator for exploring the physical resource requirements and performance demands to scale such a quantum computer to sizes capable of performing quantum algorithms beyond the limits of classical computation.

Dissociative adsorption of methane on the Cu and Zn doped (111) surface of CeO2

The development of economical heterogeneous catalysts for the activation of methane is a major challenge for the chemical industry. Screening potential candidates becomes more feasible using rational catalyst design to understand the activity of potential catalysts for CH4 activation. The focus of the present paper is the use of density functional theory to examine and elucidate the properties of doped CeO2. We dope with Cu and Zn transition metals having variable oxidation state (Cu), and a single oxidation state (Zn), and study the activation of methane. Zn is a divalent dopant and Cu can have a +1 or +2 oxidation state. Both Cu and Zn dopants have an oxidation state of +2 after incorporation into the CeO2 (111) surface; however a Hubbard +U correction (+U = 7) on the Cu 3d states is required to maintain this oxidation state when the surface interacts with adsorbed species. Dissociation of methane is found to occur locally at the dopant cations, and is thermodynamically and kinetically more favorable on Zn-doped CeO2 than Cu-doped CeO2. The origins of this lie with the Zn(II) dopant moving towards a square pyramidal geometry in the sub surface layer which facilitates the formation of two-coordinated surface oxygen atoms, that are more beneficial for methane activation on a reducible oxide surface. These findings can aid in rational experimental catalyst design for further exploration in methane activation processes.

Surface wind stress modeled for the Panama Seaway with the Community Climate System Model 3

The early Pliocene warm phase was characterized by high sea surface temperatures and a deep thermocline in the eastern equatorial Pacific. A new hypothesis suggests that the progressive closure of the Panamanian seaway contributed substantially to the termination of this zonally symmetric state in the equatorial Pacific. According to this hypothesis, intensification of the Atlantic meridional overturning circulation (AMOC) - induced by the closure of the gateway - was the principal cause of equatorial Pacific thermocline shoaling during the Pliocene. In this study, twelve Panama seaway sensitivity experiments from eight ocean/climate models of different complexity are analyzed to examine the effect of an open gateway on AMOC strength and thermocline depth. All models show an eastward Panamanian net throughflow, leading to a reduction in AMOC strength compared to the corresponding closed-Panama case. In those models that do not include a dynamic atmosphere, deepening of the equatorial Pacific thermocline appears to scale almost linearly with the throughflow-induced reduction in AMOC strength. Models with dynamic atmosphere do not follow this simple relation. There are indications that in four out of five models equatorial wind-stress anomalies amplify the tropical Pacific thermocline deepening. In summary, the models provide strong support for the hypothesized relationship between Panama closure and equatorial Pacific thermocline shoaling.

Geochemistry of surface sediment cores (Table 4)

The mineralogy and geochemistry of a suite of nine manganese nodules from the South Atlantic have been determined. The Ce/La ratios of the nodules were investigated to see if they could be used as redox indicators to trace the oxygen content of the ambient water mass and the flow path of the Antarctic Bottom Water as has previously been successfully carried out in the Pacific Ocean. The Ce/La ratios of the nodules decrease in the sequence Lazarev Sea, Weddell Sea (10.4 and 9.7)>East Georgia Basin (6.5 and 7.1)>Argentine Basin (5.0), but then increase in the Brazil Basin (6.2) and Angola Basin (9.8 and 15.1). A further decrease was observed in the Cape Basin (7.6). An extremely high Ce/La ratio of 24.4 had already been determined for nodules sampled north of the Nares Abyssal Plain in the western North Atlantic. These data reflect the more complicated pattern of bottom water flow in the South Atlantic than in the South Pacific. The penetration of more oxygenated North Atlantic Deep Water into the South Atlantic accounts for the higher Ce/La ratios in the nodules from the Angola and Brazil basins. Based on this study, the flow path of the Antarctic Bottom Water could only be traced as far north as the Argentine Basin. The unique geochemistry of nodules from the central Angola Basin (high Mn/Fe and Ce/La ratios, high contents of Ni, Cu, Zn and Mo) appears to be a function of the nature of the overlying water mass and of the multiple diagenetic sources of metals to the nodules.

(Fig. 1D, 3E) Sea surface temperature and alkenone C37:4 for sediment core MD01-2444 during the penultimate glaciation

Past glacials can be thought of as natural experiments in which variations in boundary conditions influenced the character of climate change. However, beyond the last glacial, an integrated view of orbital- and millennial-scale changes and their relation to the record of glaciation has been lacking. Here, we present a detailed record of variations in the land-ocean system from the Portuguese margin during the penultimate glacial and place it within the framework of ice-volume changes, with particular reference to European ice-sheet dynamics. The interaction of orbital- and millennial-scale variability divides the glacial into an early part with warmer and wetter overall conditions and prominent climate oscillations, a transitional mid-part, and a late part with more subdued changes as the system entered a maximum glacial state. The most extreme event occurred in the mid-part and was associated with melting of the extensive European ice sheet and maximum discharge from the Fleuve Manche river. This led to disruption of the meridional overturning circulation, but not a major activation of the bipolar seesaw. In addition to stadial duration, magnitude of freshwater forcing, and background climate, the evidence also points to the influence of the location of freshwater discharges on the extent of interhemispheric heat transport.

Eocene-Oligocene sea surface temperature and pCO2 estimates

The long-term cooling trend of the Cenozoic is punctuated by shorter-term climatic events, such as the inception of permanent ice sheets on Antarctica at the Eocene?Oligocene Transition (~33.7 Ma). Taking advantage of the excellent state of preservation of coccolith calcite in equatorial Atlantic deep-sea cores, we unveil progressive tropical warming in the Atlantic Ocean initiated 4 million years prior to Antarctic glaciation. Warming preceding glaciation may appear counterintuitive, but we argue that this long-term climatic precursor to the EOT reinforced cooling of austral high latitudes via the redistribution of heat at the surface of the oceans. We discuss this new prominent paleoceanographic and climatic feature in the context of overarching pCO2 decline and the establishment of an Antarctic circumpolar current.

Surface seawater carbonate chemistry, nutrients and phytoplankton community composition on a transect between North Sea and Arctic Ocean, 2008

This data was collected during the 'ICE CHASER' cruise from the southern North Sea to the Arctic (Svalbard) in July-Aug 2008. This data consists of coccolithophore abundance, calcification and primary production rates, carbonate chemistry parameters and ancillary data of macronutrients, chlorophyll-a, average mixed layer irradiance, daily irradiance above the sea surface, euphotic and mixed layer depth, temperature and salinity.

Benthic foraminifera in surface sediments, South Atlantic

Sixty surface sediment samples from the eastern South Atlantic Ocean including the Walvis Ridge, the Angola and Cape basins, and the Southwest African continental margin were analysed for their benthic foraminiferal content to unravel faunal distribution patterns and ecological preferences. Live (stained with Rose Bengal) and dead faunas were counted separately and then each grouped by Q-mode principal component analysis into seven principal faunal end-members. Then, multiple regression technique was used to correlate Recent assemblages with available environmental variables and to finally differentiate between four principal groups of environmental agents acting upon the generation of benthic foraminiferal assemblages: (1) seasonality of food supply and organic carbon flux rates, together with oxygen content in the pore and bottom waters; (2) lateral advection of deep-water masses; (3) bottom water carbonate corrosiveness; and (4) energetic state at the benthic boundary layer and grain size composition of the substrate. Food supply and corresponding dissolved oxygen contents in the pore and bottom waters turned out to be the most important factors which control the distribution pattern of the Recent benthic foraminifera. At the continental margin, in the zone of coastal upwelling and its mixing area, benthic foraminiferal assemblages are dominated by stenobathic high-productivity faunas, characterized by elevated standing stocks, low diversities and a large number of endobenthic living species. At the continental shelf and upper continental slope the live assemblages are characterized by Rectuvigerina cylindrica, Uvigerina peregrina s.1., Uvigerina auberiana and Rhizammina spp. while the dead assemblages are characterized by Cassidulina laevigata, Bolivina dilatata, Bulimina costata and B. mexicana. At the lower continental slope strong influence of high organic matter fluxes on the species composition is restricted to the area off the Cunene river mouth, where the live assemblage is dominated by Uvigerina peregrina s.1., the corresponding dead assemblage by Melonis barleeanum and M. zaandamae. In the adjacent areas of the lower continental slope the biocoenosis is characterized by Reophax bilocularis, and Epistominella exigua which becomes dominant in the corresponding dead assemblage. At the Walvis Ridge and in the abyssal Angola and Cape basins, where organic matter fluxes are low and highly seasonal, benthic foraminiferal assemblages reflect both the oligotrophic situation and the deep and bottom water mass configuration. The top and flanks of the Walvis Ridge are inhabited by the Rhizammina, Psammosphaera and R. bilocularis live assemblages, the corresponding dead assemblages are dominated by G. subglobosa on the ridge top and E. exigua on the flanks. Within the highly diverse E. exigua dead assemblage several associated epibenthic species coincide with the core of NADW between about 1600 and 3700 m water depth. These species include Osangularia culter, Cibicidoides kullenbergi, Melonis pompilioides, Bolivinita pseudothalmanni and Bulimina alazanensis. The assemblages of the abyssal Cape and Angola basins are characterized by Nuttallides umbonifer and a high proportion of agglutinated species. These species are adapted to very low organic matter fluxes and a carbonate corrosive environment.