Single wall carbon nanotubes loaded with Pd and NiPd nanoparticles for H2 sensing at room temperature

Pd and bimetallic Ni50Pd50 nanoparticles protected by polyvinylpyrrolidone (PVP) have been synthesized by the reduction-by-solvent method and deposited on single wall carbon nanotubes (SWCNTs) to be tested as H2 sensors. The SWCNTs were deposited by drop casting from different suspensions. The Pd nanoparticles-based sensors show a very reproducible performance with good sensitivity and very low response times (few seconds) for different H2 concentrations, ranging from 0.2% to 5% vol. H2 in air at atmospheric pressure. The influence of the metal nanoparticle composition, the quality of SWCNTs suspension and the metal loading have been studied, observing that all these parameters play an important role in the H2 sensor performance. Evidence for water formation during the H2 detection on Pd nanoparticles has been found, and its repercussion on the behaviour of the assembled sensors is discussed. The sensor preparation procedure detailed in this work has proven to be simple and reproducible to prepare cost-effective and highly efficient H2 sensors that perform very well under real application conditions.

Refinery Nonconventional Feedstocks: Influence of the Coprocessing of Vacuum Gas Oil and Low Density Polyethylene in Fluid Catalytic Cracking Unit on Full Range Gasoline Composition

Gasoline coming from refinery fluid catalytic cracking (FCC) unit is a major contributor to the total commercial grade gasoline pool. The contents of the FCC gasoline are primarily paraffins, naphthenes, olefins, aromatics, and undesirables such as sulfur and sulfur containing compounds in low quantities. The proportions of these components in the FCC gasoline invariable determine its quality as well as the performance of the associated downstream units. The increasing demand for cleaner and lighter fuels significantly influences the need not only for novel processing technologies but also for alternative refinery and petrochemical feedstocks. Current and future clean gasoline requirements include increased isoparaffins contents, reduced olefin contents, reduced aromatics, reduced benzene, and reduced sulfur contents. The present study is aimed at investigating the effect of processing an unconventional refinery feedstock, composed of blend of vacuum gas oil (VGO) and low density polyethylene (LDPE) on FCC full range gasoline yields and compositional spectrum including its paraffins, isoparaffins, olefins, napthenes, and aromatics contents distribution within a range of operating variables of temperature (500–700 °C) and catalyst-feed oil ratio (CFR 5–10) using spent equilibrium FCC Y-zeolite based catalyst in a FCC pilot plant operated at the University of Alicante’s Research Institute of Chemical Process Engineering (RICPE). The coprocessing of the oil-polymer blend led to the production of gasoline with very similar yields and compositions as those obtained from the base oil, albeit, in some cases, the contribution of the feed polymer content as well as the processing variables on the gasoline compositional spectrum were appreciated. Carbon content analysis showed a higher fraction of the C9–C12 compounds at all catalyst rates employed and for both feedstocks. The gasoline’s paraffinicity, olefinicity, and degrees of branching of the paraffins and olefins were also affected in various degrees by the scale of operating severity. In the majority of the cases, the gasoline aromatics tended toward the decrease as the reactor temperature was increased. While the paraffins and iso-paraffins gasoline contents were relatively stable at around 5 % wt, the olefin contents on the other hand generally increased with increase in the FCC reactor temperature.

X-Ray Imaging of SAPO-34 Molecular Sieves at the Nanoscale: Influence of Steaming on the Methanol-to-Hydrocarbons Reaction

The effect of a severe steaming treatment on the physicochemical properties and catalytic performance of H-SAPO-34 molecular sieves during the methanol-to-hydrocarbons (MTH) reaction has been investigated with a combination of scanning transmission X-ray microscopy (STXM), catalytic testing, and bulk characterization techniques, including ammonia temperature programmed desorption and 27Al and 29Si magic angle spinning nuclear magnetic resonance. For this purpose, two samples, namely a calcined and a steamed H-SAPO-34 catalyst powder, have been compared. It has been found that calcined H-SAPO-34 displays a high selectivity towards light olefins, yet shows a poor stability as compared to a zeolite H-ZSM-5 catalyst. Moreover, in situ STXM at the carbon K-edge during the MTH reaction allows construction of nanoscale chemical maps of the hydrocarbon species formed within the H-SAPO-34 aggregates as a function of reaction time and steam post-treatment. It was found that there is an initial preferential formation of coke precursor species within the core of the H-SAPO-34 aggregates. For longer times on stream the formation of the coke precursor species is extended to the outer regions, progressively filling the entire H-SAPO-34 catalyst particle. In contrast, the hydrothermally treated H-SAPO-34 showed similar reaction selectivity, but decreased activity and catalyst stability with respect to its calcined counterpart. These variations in MTH performance are related to a faster and more homogeneous formation of coke precursor species filling up the entire steamed H-SAPO-34 catalyst particle. Finally, the chemical imaging capabilities of the STXM method at the Al and Si K-edge are illustrated by visualizing the silicon islands at the nanoscale before and after steaming H-SAPO-34.

Sea-surface temperature reconstruction in the Southwest Pacific

Uniquely in the Southern Hemisphere the New Zealand micro-continent spans the interface between a subtropical gyre and the Subantarctic Circumpolar Current. Its 20° latitudinal extent includes a complex of submerged plateaux, ridges, saddles and basins which, in the present interglacial, are partial barriers to circulation and steer the Subtropical (STF) and Subantarctic (SAF) fronts. This configuration offers a singular opportunity to assess the influence of bottom topography on oceanic circulation through Pleistocene glacial - interglacial (G/I) cycles, its effect on the location and strength of the fronts, and its ability to generate significant differences in mixed layer thermal history over short distances. For this study we use new planktic foraminiferal based sea-surface temperature (SST) estimates spanning the past 1 million years from a latitudinal transect of four deep ocean drilling sites. We conclude that: 1. the effect of the New Zealand landmass was to deflect the water masses south around the bathymetric impediments; 2. the effect of a shallow submerged ridge on the down-current side (Chatham Rise), was to dynamically trap the STF along its crest, in stark contrast to the usual glacial-interglacial (G-I) meridional migration that occurs in the open ocean; 3. the effect of more deeply submerged, downstream plateaux (Campbell, Bounty) was to dynamically trap the SAF along its steep southeastern margin; 4. the effects of saddles across the submarine plateaux was to facilitate the development of jets of subtropical and subantarctic surface water through the fronts, forming localized downstream gyres or eddies during different phases in the G-I climate cycles; 5. the deep Pukaki Saddle across the Campbell-Bounty Plateaux guided a branch of the SAF to flow northwards during each glacial, to form a strong gyre of circumpolar surface water in the Bounty Trough, especially during the mid-Pleistocene Climate Transition (MIS 22-16) when exceptionally high SST gradients existed across the STF; 6. the shallower Mernoo Saddle, at the western end of the Chatham Rise, provided a conduit for subtropical water to jet southwards across the STF in the warmest interglacial peaks (MIS 11, 5.5) and for subantarctic water to flow northwards during glacials; 7. although subtropical or subantarctic drivers can prevail at a particular phase of a G-I cycles, it appears that the Antarctic Circumpolar Current is the main influence on the regional hydrography. Thus complex submarine topography can affect distinct differences in the climate records over short distances with implications for using such records in interpreting global or regional trends. Conversely, the local topography can amplify the paleoclimate record in different ways in different places, thus enhancing its value for the study of more minor paleoceanographic influences that elsewhere are more difficult to detect. Such sites include DSDP 594, which like some other Southern Ocean sites, has the typical late Pleistocene asymmetrical saw-tooth G-I climate pattern transformed to a gap-tooth pattern of quasi-symmetrical interglacial spikes that interrupt extended periods of minimum glacial temperatures.

Age determination and Sea surface temperature reconstruction for sediment core H214

We present sea surface temperature (SST) records with centennial-scale resolution from the Bay of Plenty, north of New Zealand. Foraminiferal assemblage-based paleo-SST estimates provide a deglacial record of SST since 16.5 14C ka. Average Holocene SSTs are 15.6°C for winter and 20.3°C for summer, whereas average glacial values were 14.2°C for winter and 19.5°C for summer. Compared to modern time, cooling of SSTs at the Last Glacial Maximum (LGM) was ~0.9°C in winter and ~1.5°C in summer. The shift from glacial to Holocene temperatures began at 14.25 14C ka, warming by ~2°C until 12.85 14C ka when temperatures dipped back to glacial values at 11.65 14C ka. The timing of this return to glacial-like SST correlates well with the Antarctic Cold Reversal (ACR) rather than the Younger Dryas and documents that the influence of the ACR extended into the subtropics of the Southern Hemisphere, at least in this region of the southwest Pacific. By 10.55 14C ka an SST maximum in summer SSTs of up to 3°C warmer than modern occurred (?24°C), after which SST dropped, remaining at present-day temperatures since 9.3 14C ka. This early Holocene climatic optimum has been widely noted in the Southern Ocean, and this record indicates that this phenomenon also extended into the subtropics to the north of New Zealand.

Water chemistry, and body temperature, swimming depth and stomach contents of Arctic char (Salvelinus alpinus) in inner Frobisher Bay, Canada

The influence of salinity, temperature and prey availability on the marine migration of anadromous fishes was determined by describing the movements, habitat use and feeding behaviours of Arctic char (Salvelinus alpinus). The objectives were to determine whether char are restricted to the upper water column of the inter-/subtidal zones due to warmer temperatures. Twenty-seven char were tracked with acoustic temperature/pressure (depth) transmitters from June to September, 2008/2009, in inner Frobisher Bay, Canada. Most detections were in surface waters (0-3 m). Inter-/subtidal movements and consecutive repetitive dives (maximum 52.8 m) resulted in extreme body temperature shifts (-0.2-18.1 °C). Approximately half of intertidal and subtidal detections were between 9-13 °C and 1-3 °C, respectively. Stomach contents and deep diving suggested feeding in both inter-/subtidal zones. We suggest that char tolerate cold water at depth to capture prey in the subtidal zone, then seek warmer water to enhance feeding/digestion physiology.

Sea surface temperature reconstruction for the Southwest Pacific Ocean

Paleoceanographic archives derived from 17 marine sediment cores reconstruct the response of the Southwest Pacific Ocean to the peak interglacial, Marine Isotope Stage (MIS) 5e (ca. 125?ka). Paleo-Sea Surface Temperature (SST) estimates were obtained from the Random Forest model-an ensemble decision tree tool-applied to core-top planktonic foraminiferal faunas calibrated to modern SSTs. The reconstructed geographic pattern of the SST anomaly (maximum SST between 120 and 132?ka minus mean modern SST) seems to indicate how MIS 5e conditions were generally warmer in the Southwest Pacific, especially in the western Tasman Sea where a strengthened East Australian Current (EAC) likely extended subtropical influence to ca. 45°S off Tasmania. In contrast, the eastern Tasman Sea may have had a modest cooling except around 45°S. The observed pattern resembles that developing under the present warming trend in the region. An increase in wind stress curl over the modern South Pacific is hypothesized to have spun-up the South Pacific Subtropical Gyre, with concurrent increase in subtropical flow in the western boundary currents that include the EAC. However, warmer temperatures along the Subtropical Front and Campbell Plateau to the south suggest that the relative influence of the boundary inflows to eastern New Zealand may have differed in MIS 5e, and these currents may have followed different paths compared to today.

Temperature measured in permafrost borehole at ICDP site 5011-3 in El'gygytgyn Crater, 2008-2011

This study focuses on the temperature field observed in boreholes drilled as part of interdisciplinary scientific campaign targeting the El'gygytgyn Crater Lake in NE Russia. Temperature data are available from two sites: the lake borehole 5011-1 located near the center of the lake reaching 400 m depth, and the land borehole 5011-3 at the rim of the lake, with a depth of 140 m. Constraints on permafrost depth and past climate changes are derived from numerical simulation of the thermal regime associated with the lake-related talik structure. The thermal properties of the subsurface needed for these simulations are based on laboratory measurements of representative cores from the quaternary sediments and the underlying impact-affected rock, complemented by further information from geophysical logs and data from published literature. The temperature observations in the lake borehole 5011-1 are dominated by thermal perturbations related to the drilling process, and thus only give reliable values for the lowermost value in the borehole. Undisturbed temperature data recorded over more than two years are available in the 140 m deep land-based borehole 5011-3. The analysis of these observations allows determination of not only the recent mean annual ground surface temperature, but also the ground surface temperature history, though with large uncertainties. Although the depth of this borehole is by far too insufficient for a complete reconstruction of past temperatures back to the Last Glacial Maximum, it still affects the thermal regime, and thus permafrost depth. This effect is constrained by numerical modeling: assuming that the lake borehole observations are hardly influenced by the past changes in surface air temperature, an estimate of steady-state conditions is possible, leading to a meaningful value of 14 ± 5 K for the post-glacial warming. The strong curvature of the temperature data in shallower depths around 60 m can be explained by a comparatively large amplitude of the Little Ice Age (up to 4 K), with low temperatures prevailing far into the 20th century. Other mechanisms, like varying porosity, may also have an influence on the temperature profile, however, our modeling studies imply a major contribution from recent climate changes.

Sea-surface temperature reconstructions for the Quaternary western Atlantic

Paleotemperature estimates calculated by the SIMMAX Modern Analog Technique are presented for two gravity cores from the Rio Grande Rise, one from the Brazil Slope, and one from the Ceara Rise. The estimates are based on comparisons between modern and fossil planktonic foraminiferal assemblages and were carried out on samples from Quaternary sediments. Estimated warm-season temperatures from the Rio Grande Rise (at approx. 30° S) range from around 19°C to 24°C, with some coincidence of warm peaks with interglacial stages. The temperature estimates (also warm-season) from the more tropical Brazil Slope (at approx. 8° S) and Ceara Rise (at approx. 4° N) cores are more stable, remaining between 26°C and 28°C throughout most of their lengths. This fairly stable situation in the tropical western Atlantic is interrupted in oxygen isotope stage 6 by a significant drop of 2-3°C in both of these cores. Temperature estimates from the uppermost samples in all cores compare very well to the modern-day measured values. Affinities of some foraminiferal species for warmer or cooler surface temperatures are identified within the temperature range of the examined samples based on their abundance values. Especially notable among the warmer species are, Globorotalia menardii, Globigerinita glutinata, Globigerinoides ruber, and Globigerinoides sacculifer. Species indicative of cooler surface temperatures include Globorotalia inflata, Globigerina bulloides, Neogloboquadrina pachyderma, and Globigerina falconensis. A cluster analysis was carried out to assist in understanding the degree of variation which occurs in the foraminiferal assemblages, and how temperature differences influence the faunal compositions of the samples. It is demonstrated that fairly similar samples may have unexpectedly different estimated temperatures due to small differences in key species and, conversely, quite different assemblages can result in similar or identical temperature estimates which confirms that other parameters than just temperature affect faunal content.

(Table 1) Sea surface temperature reconstruction for eastern equatorial Pacific surface sediment samples

Significant uncertainties persist in the reconstruction of past sea surface temperatures in the eastern equatorial Pacific, especially regarding the amplitude of the glacial cooling and the details of the post-glacial warming. Here we present the first regional calibration of alkenone unsaturation in surface sediments versus mean annual sea surface temperatures (maSST). Based on 81 new and 48 previously published data points, it is shown that open ocean samples conform to established global regressions of Uk'37 versus maSST and that there is no systematic bias from seasonality in the production or export of alkenones, or from surface ocean nutrient concentrations or salinity. The flattening of the regression at the highest maSSTs is found to be statistically insignificant. For the near-coastal Peru upwelling zone between 11-15°S and 76-79°W, however, we corroborate earlier observations that Uk'37 SST estimates significantly over-estimate maSSTs at many sites. We posit that this is caused either by uncertainties in the determination of maSSTs in this highly dynamic environment, or by biasing of the alkenone paleothermometer toward El Niño events as postulated by Rein et al. (2005).

The North Pacific biological pump: Rates, efficiency and influence on ocean carbon uptake

Thesis (Ph.D.)--University of Washington, 2016-05

Assessing the seasonal influence of sewage and agricultural nutrient inputs in a subtropical river estuary

A combination of physical and chemical measurements and biological indicators identified nutrient impacts throughout an Australian subtropical river estuary. This was a balance of sewage inputs in the lower river and agricultural inputs in the mid-upper river, the combined influence being greater in the wet season due to greater agricultural surface runoff. Field sampling in the region was conducted at 6 sites within the river, over 5 surveys to encapsulate both wet and dry seasonal effects. Parameters assessed were tissue nitrogen (N) contents and delta(15)N signatures of mangroves and macroalgae, phytoplankton nutrient addition bioassays, and standard physical and chemical variables. Strong spatial (within river) and temporal (seasonal) variability was observed in all parameters. Poorest water quality was detected in the middle (agricultural) region of the river in the wet season, attributable to large diffuse inputs in this region. Water quality towards the river mouth remained constant irrespective of season due to strong oceanic flushing. Mangrove and macroalgal tissue delta(15)N and %N proved a successful combination for discerning sewage and agricultural inputs. Elevated delta(15)N and %N represented sewage inputs, whereas low delta(15)N and elevated %N was indicative of agricultural inputs. Phytoplankton bioassays found the system to be primarily responsive to nutrient additions in the warmer wet season, with negligible responses observed in the cooler dry season. These results indicate that the Tweed River is sensitive to the different anthropogenic activities in its catchment and that each activity has a unique influence on receiving water quality.

Layered silicate nanocomposites based on various high-functionality epoxy resins: The influence of an organoclay on resin cure

The influence of an organically modified clay on the curing behavior of three epoxy systems widely used in the aerospace industry and of different structures and functionalities, was studied. Diglycidyl ether of bisphenol A (DGEBA), triglycidyl p-amino phenol (TGAP) and tetraglycidyl diamino diphenylmethane (TGDDM) were mixed with an octadecyl ammonium ion modified organoclay and cured with diethyltoluene diamine (DETDA). The techniques of dynamic mechanical thermal analysis (DMTA), chemorheology and differential scanning calorimetry (DSC) were applied to investigate gelation and vitrification behavior, as well as catalytic effects of the clay on resin cure. While the formation of layered silicate nanocomposite based on the bifunctional DGEBA resin has been previously investigated to some extent, this paper represents the first detailed study of the cure behavior of different high performance, epoxy nanocomposite systems.