Promoter effect of sodium in graphene-supported Ni and Ni–CeO2 catalyst for the low-temperature WGS reaction

The low temperature water–gas shift (WGS) reaction has been studied over Ni–CeO2/Graphene and Ni/Graphene. The catalysts were prepared with 5 wt.% Ni and 20 wt.% CeO2 loadings, by deposition-precipitation employing sodium hydroxide and urea as precipitating agents. The materials were characterized by TEM, powder X-ray diffraction, Raman spectroscopy, H2-temperature-programmed reduction and X-ray photoelectron spectroscopy (XPS). The characterization and the reaction results indicated that the interaction between the active species and the support is higher than with activated carbon, and this hinders the reducibility of ceria and thus the catalytic performance. On the other hand, the presence of residual sodium in samples prepared by precipitation with NaOH facilitated the reduction of ceria. The catalytic activity was highly improved in the presence of sodium, what can be explained on the basis of an associative reaction mechanism which is favored over Ni-O-Na entities.

Functionalization of carbon nanotubes using aminobenzene acids and electrochemical methods. Electroactivity for the oxygen reduction reaction

Functionalized carbon nanotubes (CNTs) using three aminobenzene acids with different functional groups (carboxylic, sulphonic, phosphonic) in para position have been synthesized through potentiodynamic treatment in acid media under oxidative conditions. A noticeable increase in the capacitance for the functionalized carbon nanotubes mainly due to redox processes points out the formation of an electroactive polymer thin film on the CNTs surface along with covalently bonded functionalities. The CNTs functionalized using aminobenzoic acid rendered the highest capacitance values and surface nitrogen content, while the presence of sulfur and/or phosphorus groups in the aminobenzene structure yielded a lower functionalization degree. The oxygen reduction reaction (ORR) activity of the functionalized samples was similar to that of the parent CNTs, independently of the functional group present in the aminobenzene acid. Interestingly, a heat treatment in N2 atmosphere with a very low O2 concentration (3125 ppm) at 800 °C of the CNTs functionalized with aminobenzoic acid produced a material with high amounts of surface oxygen and nitrogen groups (12 and 4% at., respectively), that seem to modulate the electron-donor properties of the resulting material. The onset potential and limiting current for ORR was enhanced for this material. These are promising results that validates the use of electrochemistry for the synthesis of novel N-doped electrocatalysts for ORR in combination with adequate heat treatments.

Design of Activated Carbon/Activated Carbon Asymmetric Capacitors

Supercapacitors are energy storage devices that offer a high power density and a low energy density in comparison with batteries. Their limited energy density can be overcome by using asymmetric configuration in mass electrodes, where each electrode works within their maximum available potential window, rendering the maximum voltage output of the system. Such asymmetric capacitors are optimized using the capacitance and the potential stability limits of the electrodes, with the reliability of the design largely depending on the accuracy and the approach taken for the electrochemical characterization. Therefore, the performance could be lower than expected and even the system could break down, if a well thought out procedure is not followed. In this work, a procedure for the development of asymmetric supercapacitors based on activated carbons is detailed. Three activated carbon materials with different textural properties and surface chemistry have been systematically characterized in neutral aqueous electrolyte. The asymmetric configuration of the masses of both electrodes in the supercapacitor has allowed to cover a higher potential window, resulting in an increase of the energy density of the three devices studied when compared with the symmetric systems, and an improved cycle life.

Catalytic wet peroxide oxidation: a route towards the application of hybrid magnetic carbon nanocomposites for the degradation of organic pollutants. A review

Several motivations have prompted the scientific community towards the application of hybrid magnetic carbon nanocomposites in catalytic wet peroxide oxidation (CWPO) processes. The most relevant literature on this topic is reviewed, with a special focus on the synergies that can arise from the combination of highly active and magnetically separable iron species with the easily tuned properties of carbon-based materials. These are mainly ascribed to increased adsorptive interactions, to good structural stability and low leaching levels of the metal species, and to increased regeneration and dispersion of the active sites, which are promoted by the presence of the carbon-based materials in the composites. The most significant features of carbon materials that may be further explored in the design of improved hybrid magnetic catalysts are also addressed, taking into consideration the experimental knowledge gathered by the authors in their studies and development of carbon-based catalysts for CWPO. The presence of stable metal impurities, basic active sites and sulphur-containing functionalities, as well as high specific surface area, adequate porous texture, adsorptive interactions and structural defects, are shown to increase the activity of carbon materials when applied in CWPO, while the presence of acidic oxygen-containing functionalities has the opposite effect.

Synthesis of glycerol-based carbon materials as environmental application

Crude glycerol, obtained from the biodiesel production, is actually an abundant and low-cost feedstock, making the preparation of carbonaceous materials by partial carbonization and sulfonation of this by-product an interesting research focus. Bearing this in mind, the aim of this study is to explore several types of glycerol-based carbon materials synthesized by partial carbonization of glycerol in concentrated sulphuric acid solution for the removal of flumequine and tetracycline from aqueous solutions. This study is focused on the synthesis and application of glycerol-based carbon materials as adsorbents for the removal of the antibiotic compounds flumequine and tetracycline from aqueous solution. The different synthesized materials were labelled as GBCM followed by a subscript number corresponding to the activation temperature in oC (i.e., GBCM200, GBCM300, and GBCM350)

Calcium carbonate, total and organic carbon and accumulation rate characteristics at DSDP Leg 78A Holes

Bulk sediment accumulation rates and carbonate and carbonate-free accumulation rates corrected for tectonic tilting have been calculated for Leg 78A sediments. These rates are uniformly low, ranging from 0.1 to 6.8 g/(cm**2 x 10**3 yr.), reflecting the pelagic-hemipelagic nature of all the sediments drilled in the northern Lesser Antilles forearc. Rates calculated for Sites 541 and 542 [0.6-6.8 g/(cm**2 x 10**3 yr.)], located on the lower slope of the accretionary prism, are significantly greater than the Neogene rates calculated for oceanic reference Site 543 [0.1-2.4 g/(cm**2 x 10**3)]. This difference could be the result of (1) tectonic thickening of accretionary prism sediments due to folding, small-scale faulting, and layer-parallel shortening; (2) deposition in shallower water farther above the CCD (carbonate compensation depth) resulting in preservation of a greater percentage of calcareous microfossils; or (3) a greater percentage of foraminiferal sediment gravity flows. Terrigenous turbidites are not documented in the Leg 78A area because of (1) great distance from South American sources; (2) damming effects of east-west trending tectonic elements; and (3) location on the Tiburon Rise (Site 543). This lack of terrigenous material, characteristic of intraoceanic convergent margins, suggests that published sedimentation models for active continental convergent margins with abundant terrigenous influxes are not applicable to intraoceanic convergent margin settings.

Stable oxygen and carbon isotope of foraminifera from DSDP Leg 90 sites

High-resolution oxygen and carbon isotope stratigraphy is presented for Miocene to early Pliocene sequences at three DSDP sites from the Lord Howe Rise, southwest Pacific, at water depths ranging from 1,300 to 2,000 m. Site 588 is located in the warm subtropics (~26°S), whereas Sites 590 and 591 are positioned in transitional (northern temperate) water masses (~31°S). Benthic foraminiferal oxygen and carbon isotope analyses were conducted on all sites; planktonic foraminiferal isotope data were generated for Site 590 only. Sample resolution in these sequences is on the order of 50,000 yr. or better. The chronological framework employed in this study is based largely upon ages assigned to Neogene calcareous nannoplankton boundaries. The benthic oxygen isotope record exhibits several major features during the Neogene. During most of the early Miocene, delta18O values were relatively low, reaching minimum values in the late early Miocene (19.5 to 16.5 Ma), and recording the climax of Neogene warmth. This was followed by a major increase in benthic delta18O values between ~16.5 and 13.5 Ma, which is interpreted as representing major, permanent accumulation of the East Antarctic ice sheet and cooling of bottom waters. During the 3 m.y. 18O enrichment, surface waters at these middle latitudes warmed between 16 and 14.5 Ma. During the remainder of the middle and late Miocene, benthic delta18O values exhibit distinct fluctuations, but the average value remained unchanged. The isotopic data show two distinct episodes of climatic cooling close to the middle/late Miocene boundary. The earliest of these events occurred between 12.5 and 11.5 Ma in the latest middle Miocene. The second cooling event occurred from 11 to 9 Ma, and is marked by some of the highest delta18O values of the entire Miocene. This was followed by relative warmth during the middle part of the late Miocene. The latest Miocene and earliest Pliocene (6.2 to 4.5 Ma) were marked by relatively high delta18O values, indicating increased cooling and glaciation. During the middle Pliocene, at about 3.4 Ma, a 0.4 per mil increase in benthic delta18O documents a net increase in average global ice volume and cooling of bottom waters. During this interval of increased glaciation, surface waters warmed by 2-3°C in southern middle-latitude regions. During the late Pliocene, between 2.6 and 2.4 Ma, a further increase in delta18O occurred; this has been interpreted by previous workers as heralding the onset of Northern Hemisphere glaciation. Surface-water warming in the middle latitudes occurred in association with major high-latitude glacial increases in the early middle Miocene (16-14 Ma), middle Pliocene (-3.5 Ma), and late Pliocene (~2.4 Ma). These intervals were also marked by increases in the vertical temperature gradient in the open ocean. Intersite correlation is enhanced by using carbon isotope stratigraphy. The great similarity of the delta13C time-series records within and between ocean basins and with water depth clearly indicates that changes in oceanwide average delta13C of [HCO3]- in seawater dominated the records, rather than local effects. Broad changes in the Neogene delta13C record were caused largely by transfer of organic carbon between continental and oceanic reservoirs. These transfers were caused by marine transgressions and regressions on the continental margins. The dominant feature of Neogene delta13C stratigraphy is a broad late early to early middle Miocene increase of about lâ between ~19 and 14.5 Ma. This trend occurred contemporaneously with a period of maximum coastal onlap (transgression) and maximum Neogene climatic warmth. The delta13C trend terminated during the expansion of the Antarctic ice sheet and associated marine regression. The latest Miocene carbon isotope shift (of up to - 0.75 per mil) at 6.2 Ma is clearly recorded in all sites examined and was followed by relatively low values during the remainder of the Neogene. This shift was caused by a glacioeustatic sealevel lowering that exposed continental margins via regression and ultimately increased the flux of organic carbon to the deep sea. An increase in delta13C values during the early Pliocene (~5 to 4 Ma) resulted from marine transgression during a time of global warmth.

Total organic carbon, delta13C, biomarker, gas compilations and hopanoids analysis from IODP Sites 307-U1317 and 307-U1318

During the Integrated Ocean Drilling Program (IODP) Expedition 307 for the first time a cold-water coral carbonate mound was drilled down through its base into the underlying sediments. In the current study, sample material from within and below Challenger Mound, located in the Belgica carbonate mound province in the Porcupine Basin offshore Ireland, was investigated for its distribution of microbial communities and gas composition using biogeochemical and geochemical approaches to elucidate the question on the initiation of carbonate mounds. Past and living microbial populations are lower in the mound section compared to the underlying sediments or sediments of an upslope reference site. A reason for this might be a reduced substrate feedstock, reflected by low total organic carbon (TOC) contents, in the once coral dominated mound sequence. In contrast, in the reference site a lithostratigraphic sequence with comparatively high TOC contents shows higher abundances of both past and present microbial communities, indicating favourable living conditions from time of sedimentation until today. Composition and isotopic values of gases below the mound base seem to point to a mixed gas of biogenic and thermogenic origin with a higher proportion of biogenic gas. Oil-derived hydrocarbons were not detected at the mound site. This suggests that at least in the investigated part of the mound base the upward flow of fossil hydrocarbons, being one hypothesis for the initiation of the formation of carbonate mounds, seems to be only of minor significance.

Valve concentration of Ethmodiscus sp. and carbon in sediment core GeoB3801-6

Within generally calcareous sediment sequences, layers of variable thickness of the giant diatom Ethmodiscus were found in five cores recovered in the Subtropical South Atlantic between 23° and 33°S from both sides of the Mid-Atlantic Ridge. Two types of oozes occur: (almost) monospecific layers of Ethmodiscus and layers dominated by Ethmodiscus, with several accompanying tropical/subtropical, oligotrophic-water diatoms. The two thickest Ethmodiscus layers occur in GeoB3801-6 around 29°S, and accumulated during late MIS 14 and MIS 12, respectively. Downcore concentrations of Ethmodiscus valves range between 3.4 10 4 and 2.3 10 7 valves g -1. We discuss the ooze formation in the context of migration of frontal systems and changes in the thermohaline circulation. The occurrence of Ethmodiscus oozes in sediments underlying the present-day pelagic, low-nutrient waters is associated with a terminal event of the Mid-Pleistocene Transition at around 530 ka, when the ocean circulation rearranged after a period of reduced NADW production.

(Table 1) Stable carbon isotope record and calculated recycled DIC for sediment core ANDRA_HTM102

The prominent negative stable carbon isotope excursion in both carbonate and organic carbon recorded in organic-rich sediments deposited during the Toarcian oceanic anoxic event (OAE) has commonly been explained by recycling of 13C-depleted CO2 (the so-called Küspert model). More recently, the massive release of 13C-depleted methane or other forms of 13C-depleted carbon was also proposed to account for the observed negative d13C excursions in organic carbon of terrigenous as well as of marine origin. The occurrence of diagenetic products of the carotenoid isorenieratene (isorenieratane and other aryl isoprenoids) in Toarcian black shales has been regarded as supporting evidence for the Küspert hypothesis as they point to strong stratification of the epicontinental seas. A section of a drill core straddling the Toarcian of the Paris Basin (Cirfontaine-en-Ornois) contained intact isorenieratane, providing evidence that photosynthetic green sulphur bacteria were present at the time of deposition, even prior to the OAE. However, the isorenieratane abundances are very low in the section where the negative d13C excursion in organic carbon and phytane, a chemical fossil derived from chlorophyll, occurs. The abundance of the isorenieratene derivatives increases, once the d13C records have shifted to more positive values. The d13C of isorenieratane (generally circa -13.1 ± 0.5 per mil) indicates that the respired CO2 contribution at the chemocline was low and is thus not likely to be the main cause of the prominent up to 7per mil negative d13C shift recorded in Toarcian organic carbon records.

(Tab. XIII.1) TOC content, carbonate content, carbonate mineralogy, percentage of total carbonate, aragonite, low magnesium calcium, and high magnesium calcium, and grain-size contents from samples from the Golfe d'Arguin and from the Western Sahara

Modern carbonate sedimentation takes place on the northern Mauritanian shelf (20°N), where typical tropical components (e.g. hermatypic reefs, calcareous green algae) are absent. Such deposits are reminiscent of extratropical sediment in the geological record. The tropical open shelf of Mauritania is influenced by large siliciclastic dust input and upwelling, highly fertilizing the ocean, as well as strongly limiting the light penetration. In this context, temperature does not appear to be the steering factor of carbonate production. This thesis describes the depositional system of the Golfe d'Arguin off Mauritania and focuses on environmental conditions that control the depositional pattern, in particular carbonate production. The description of this modern analogue provides a tool for paleoenvironmental interpretation of ancient counterparts. The Golfe d'Arguin is a broad shallow shelf comprising extensive shoals (<10 m water depth; i.e. the Banc d'Arguin) on the inner shelf where waters warm up. The sediments collected in water depths between 4 and 600 m are characterized by mixed carbonate and siliciclastic (dust) deposits. They vary from clean coarse-grained, almost pure carbonate loose sediments to siliciclastic-dominated fine-grained sediments. The carbonate content and sediment grain size show a north-south decreasing pattern through the Golfe d'Arguin and are controlled by the hydraulic regime influenced by wind-driven surface currents, swell, and tidal currents. The carbonate grain association is heterozoan. Components include abundant molluscs, foraminifers, and worm tubes, as well as barnacles and echinoderms, elements that are also abundant in extratropical sediments. The spatial distribution of the sedimentary facies of the Golfe d'Arguin does not display a depth zonation but rather a mosaic (i.e. patchy distribution). The depth and climatic signatures of the different sedimentary facies are determined by taxonomic and ecological investigations of the carbonate-secreting biota (molluscs and foraminifers). While certain planktonic foraminifers and molluscs represent upwelling elements, other components (e.g. mollusc and benthic foraminifer taxa) demonstrate the tropical origin of the sediment. The nutrient-rich (and thus also low light-penetration) conditions are reflected in the fact that symbiotic and photosynthetic carbonate-producing organisms (e.g. hermatypic corals) are absent. The Mauritanian deposits represent an environment that is rare in the modern world but might have been more common in the geological past when global temperatures were higher. Taxonomic and ecological studies allow for distinguishing carbonate sediments formed under either tropical high-nutrient or extratropical conditions, thus improving paleoclimate reconstruction.

Description of sediments, epoch, calcium carbonate, orgnic carbon, geolipids and mass accumulation rate at DSDP Holes 92-597A, 92-600 and 92-601B

Low concentrations of organic carbon in slowly accumulating sediments from Sites 597, 600, and 601 reflect a history of low marine productivity in the subtropical South Pacific since late Oligocene times. The distributions of n-alkanes, n-alkanoic acids, and n-alkanols provide evidence of the microbial alteration of sediment organic matter. Landderived hydrocarbons, possibly from eolian transport, dominate n-alkane distributions in these samples.

(Table 1) Concentrations of CaCO3 and organic carbon, organic matter atomic C/N ratios and delta13C values of sediment samples from Site DSDP 594

CaCO3 and total organic carbon concentrations, organic matter C/N and carbon isotope ratios, and sediment accumulation rates in late Quaternary sediments from DSDP Site 594 provide information about glacial-interglacial variations in the delivery of organic matter to the Chatham Rise offshore of southeastern New Zealand. Low C/N ratios and nearly constant organic delta13C values of ?23? indicate that marine production dominates organic matter supply in both glacial and interglacial times during oxygen isotope stages 1 through 6 (0-140 ka) and 17 through 19 (660-790 ka). Increased organic carbon mass accumulation rates in isotope stages 2, 4, 6, and 18 record enhanced marine productivity during glacial maxima. Excursions of organic delta13C values to ca. ?29? in portions of isotope stage 2 suggest that the local concentration of dissolved CO2 was occasionally elevated during the last glacial maximum, probably as a result of short periods of lowered sea-surface temperature. Dilution of carbonates by clastic continental sediment generally increases at this location during glacial maxima, but enhanced delivery of land-derived organic matter does not accompany the increased accumulation of clastic sediments.

Stable carbon and oxygen isotope composition of benthic foraminifera

Seventeen surface sediment samples from the North Atlantic Ocean off NE-Greenland between 76° and 81°N, and nine samples from the South Atlantic Ocean close to Bouvet Island between 48° and 55°S were taken with the aid of a Multiple Corer and investigated for their live (Rose Bengal stained) benthic foraminiferal content within the upper 15 cm of sediment. Preferentially endobenthic Melonis barleeanum, Melonis zaandami, and Bulimina aculeata as well as preferentially epibenthic Lobatula lobatula were counted from 1-cm-thick sediment slices each and analyzed for stable carbon and oxygen isotopic compositions of their calcareous tests. Live and dead specimens were counted and measured separately. The carbon isotopic composition of the foraminifera was compared to that of the dissolved inorganic carbon (DIC) of simultaneously sampled bottom water. During a period of one month, one station off NE-Greenland was replicately sampled once every week and samples were processed as above. Live specimens of Lobatula lobatula are confined to the uppermost two centimeters of sediment. Live specimens of Melonis spp. are found down to 8 cm within the sediment but with a distinct sub-surface maximum between 2 and 5 cm. The down-core distribution of live Bulimina aculeata shows a distinct surface maximum in the top centimeter and constant but low numbers down to 11-cm subbottom depth. The average stable carbon isotopic composition (d13C versus per mil PDB) of live Lobatula lobatula off NE-Greenland is by 0.4±0.1 per mil higher than the d13CDIC of the ambient bottom water at the time of sampling. There is evidence that this species calcify before the ice-free season, when bottom water d13CDIC is supposed to be higher. This would reconfirm the one-to-one relationship between d13C of ambient water DIC and cibicids, widely used by paleoceanographers. Live Melonis barleeanum show a negative offset from bottom water DIC of -1.7±0.6 per mil in the uppermost sediment and of -2.2±0.5 per mil in 3-4-cm subbottom depth. All d13C values of live Melonis spp. decrease within the upper four centimeters, regardless of the time of sampling and site investigated. The offset of live Bulimina aculeata from bottom water d13CDIC values of 8 stations rather constantly amounts to -0.6±0.1 per mil, no matter what subbottom depth the specimens are from. At one station however, where is strong indication of elevated organic carbon flux, the negative offset averaged over all sub-bottom depths increases to -1.5±0.2 per mil. Buliminids actively move within the sediment and by this either record an average isotope signal of the pore water or the signal of one specific calcification depth. The recorded signal, however, depends on the organic carbon flux and reflects general but site-specific pore water d13CDIC values. If compared with epibenthic d13C values from the same site, not influenced by pore water and related phytodetritus layer effects, Buliminad13C values bear some potential as a paleoproductivity proxy. Specimens of Melonis spp. seem to prefer a more static way of life and calcify at different but individually fix depths within the sediment. Although live specimens thus record a stratified pore water d13C signal, there is no means yet to correct for bioturbational and early diagenetic effects in fossil faunas.