The structural permeability of concrete at cryogenic temperatures

The thesis describes a programme of research designed to identify concretes for application at cryogenic temperature, in particular for storage of Liquefield Natural Gas which is maintained at a temperature of -165oC. The programme was undertaken in two stages. Stage 1 involved screening tests on seventeen concrete mixes to investigate the effects of strength grade (and water/cement ratio), air entrainment, aggregate type and cement type. Four mixes were selected on the basis of low temperature strength, residual strength after thermal cycling and permeability at ambient temperature. In Stage 2 the selected mixes were subjected to a comprehensive range of tests to measure those properties which determine the leak tightness of a concrete tank at temperatures down to -165oC. These included gas permeability; tensile strength, strain capacity, thermal expansion coefficient and elastic modulus, which in combination provide a measure of resistance to cracking; and bond to reinforcement, which is one of the determining factors regarding crack size and spacing. The results demonstrated that the properties of concrete were generally enhanced at cryogenic temperature, with reduced permeability, reduced crack proneness and, by virtue of increased bond to reinforcement, better control of cracking should it occur. Of the concretes tested, a lightweight mix containing sintered PFA aggregate exhibited the best performance at ambient and cryogenic temperature, having appreciably lower permeability and higher crack resistance than normal weight concretes of the same strength grade. The lightweight mix was most sensitive to thermal cycling, but there was limited evidence that this behaviour would not be significant if the concrete was prestressed. Relationships between various properties have been identified, the most significant being the reduction in gas permeability with increasing strain capacity. The structural implications of the changing properties of the concrete have also been considered.

The effects of substrate water availability on the isolation and growth of fungi

The work reported in this thesis was carried out to contribute to the knowledge of the effects of substrate water availability or water activity (a ) on fungal growth parameters and its implications in the preparationw of materials susceptible to biodeterioration. Fungi were isolated from soils of different ecological sites at a range of substrate aw levels controlled by sodium chloride (NaCl). Three groups of fungi were isolated : firstly, those isolated only at high a (aw about 0.997).secondly, those isolated at high and decreasing aw (aw 0.997 to 0.85) and finally, those isolated at only decreased aw (aw O.95 to 0.80). From these isolations, test fungi were selected to study the effects of pH, temperature, exo-enzyme production and biocide efficacy at decreased aw levels, with glycerol and NaCl as a controlling solutes. The linear extension rates of the fungi increased at all test pH values near optimum a of growth. Test fungi of the Aspergillus glaucus group were found to be most resistant to low aw. Growth and survival of vegetative and fruiting bodies at elevated temperatures were enhanced with the addition of a controlling solutes. A. flavus, A. fumigatus displayed high heat resistance and A. amstelodami, A. versicolor and Penicillium citrinum displayed low heat resistance at high aw levels and vice versa at low aw levels. Amylase, lipase and protease activities were studied at lowered aw , using modifications of the test tube method of Raute11a and Cowling. Amylase and protease production in most xerophilic fungi ceased around 0.80 aw , but lipase production in some xerophilic fungi, including A. glatlcus fungi, was up to and including 0.70 aw with g1ycero1.

Monte Carlo and molecular dynamics simulations of methane in potassium montmorillonite clay hydrates at elevated pressures and temperatures

The structure and dynamics of methane in hydrated potassium montmorillonite clay have been studied under conditions encountered in sedimentary basin and compared to those of hydrated sodium montmorillonite clay using computer simulation techniques. The simulated systems contain two molecular layers of water and followed gradients of 150 barkm-1 and 30 Kkm-1 up to a maximum burial depth of 6 km. Methane particle is coordinated to about 19 oxygen atoms, with 6 of these coming from the clay surface oxygen. Potassium ions tend to move away from the center towards the clay surface, in contrast to the behavior observed with the hydrated sodium form. The clay surface affinity for methane was found to be higher in the hydrated K-form. Methane diffusion in the two-layer hydrated K-montmorillonite increases from 0.39×10-9 m2s-1 at 280 K to 3.27×10-9 m2s-1 at 460 K compared to 0.36×10-9 m2s-1 at 280 K to 4.26×10-9 m2s-1 at 460 K in Na-montmorillonite hydrate. The distributions of the potassium ions were found to vary in the hydrates when compared to those of sodium form. Water molecules were also found to be very mobile in the potassium clay hydrates compared to sodium clay hydrates. © 2004 Elsevier Inc. All All rights reserved.

In-situ XPS study on the reducibility of Pd-promoted Cu/CeO2 catalysts for the oxygen-assisted water-gas-shift reaction

Cu/CeO2, Pd/CeO2, and CuPd/CeO2 catalysts were prepared and their reduction followed by in-situ XPS in order to explore promoter and support interactions in a bimetallic CuPd/CeO2 catalyst effective for the oxygen-assisted water-gas-shift (OWGS) reaction. Mutual interactions between Cu, Pd, and CeO2 components all affect the reduction process. Addition of only 1 wt% Pd to 30 wt% Cu/CeO2 greatly enhances the reducibility of both dispersed CuO and ceria support. In-vacuo reduction (inside XPS chamber) up to 400 °C results in a continuous growth of metallic copper and Ce3+ surface species, although higher temperatures results in support reoxidation. Supported copper in turn destabilizes metallic palladium metal with respect to PdO, this mutual perturbation indicating a strong intimate interaction between the Cu–Pd components. Despite its lower intrinsic reactivity towards OWGS, palladium addition at only 1 wt% loading significantly improved CO conversion in OWGS reaction over a monometallic 30 wt% Cu/CeO2 catalysts, possibly by helping to maintain Cu in a reduced state during reaction.

Molecular dynamics simulation of methane in sodium montmorillonite clay hydrates at elevated pressures and temperatures

Computer simulation has been used to study the structure and dynamics of methane in hydrated sodium montmorillonite clays under conditions encountered in sedimentary basins. Systems containing approximately one, two, three and four molecular layers of water have followed gradients of 150 bar km-1 and 30Kkm-1, to a maximum burial depth of 6 km (900 bar and 460 K). Methane is coordinated to approximately 19 oxygen atoms, of which typically 6 are provided by the clay surface. Only in the three- and four-layer hydrates is methane able to leave the clay surface. Diffusion depends strongly on the porosity (water content) and burial depth: self-diffusion coefficients are in the range 0.12 × 10-9m2s-1 for water and 0.04 × 10−9m2s−1 < D < 8.64 × 10−9m2s−1 for methane. Bearing in mind that porosity decreases with burial depth, it is estimated that maximum diffusion occurs at around 3 km. This is in good agreement with the known location of methane reservoirs in sedimentary basins.

Exploratory catalyst screening studies on the base free conversion of glycerol to lactic acid and glyceric acid in water using bimetallic Au-Pt nanoparticles on acidic zeolites

The base free oxidation of glycerol with molecular oxygen in water using bimetallic Au-Pt catalysts on three different acidic zeolite supports (H-mordenite, H-β and H-USY) was explored in a batch setup. At temperatures between 140 and 180 °C, lactic acid formation was significant and highest selectivity (60 % lactic acid at 80 % glycerol conversion) was obtained using Au-Pt/USY-600 (180 °C). A selectivity switch to glyceric acid (GLYA) was observed when the reactions were performed at 100 °C. Highest conversion and selectivity towards GLYA were obtained with Au-Pt/H-β as the catalyst (68 % selectivity at 68 % conversion).

Fractal analysis of flocs formed in edible oil -water emulsions by image analysis techniques

Edible oil is an important contaminant in water and wastewater. Oil droplets smaller than 40 μm may remain in effluent as an emulsion and combine with other contaminants in water. Coagulation/flocculation processes are used to remove oil droplets from water and wastewater. By adding a polymer at proper dose, small oil droplets can be flocculated and separated from water. The purpose of this study was to characterize and analyze the morphology of flocs and floc formation in edible oil-water emulsions by using microscopic image analysis techniques. The fractal dimension, concentration of polymer, effect of pH and temperature are investigated and analyzed to develop a fractal model of the flocs. Three types of edible oil (corn, olive, and sunflower oil) at concentrations of 600 ppm (by volume) were used to determine the optimum polymer dosage and effect of pH and temperature. To find the optimum polymer dose, polymer was added to the oil-water emulsions at concentration of 0.5, 1.0, 1.5, 2.0, 3.0 and 3.5 ppm (by volume). The clearest supernatants obtained from flocculation of corn, olive, and sunflower oil were achieved at polymer dosage of 3.0 ppm producing turbidities of 4.52, 12.90, and 13.10 NTU, respectively. This concentration of polymer was subsequently used to study the effect of pH and temperature on flocculation. The effect of pH was studied at pH 5, 7, 9, and 11 at 30°C. Microscopic image analysis was used to investigate the morphology of flocs in terms of fractal dimension, radius of oil droplets trapped in floc, floc size, and histograms of oil droplet distribution. Fractal dimension indicates the density of oil droplets captured in flocs. By comparison of fractal dimensions, pH was found to be one of the most important factors controlling droplet flocculation. Neutral pH or pH 7 showed the highest degree of flocculation, while acidic (pH 5) and basic pH (pH 9 and pH 11) showed low efficiency of flocculation. The fractal dimensions achieved from flocculation of corn, olive, and sunflower oil at pH 7 and temperature 30°C were 1.2763, 1.3592, and 1.4413, respectively. The effect of temperature was explored at temperatures 20°, 30°, and 40°C and pH 7. The results of flocculation of oil at pH 7 and different temperatures revealed that temperature significantly affected flocculation. The fractal dimension of flocs formed in corn, olive and sunflower oil emulsion at pH 7 and temperature 20°, 30°, and 40°C were 1.82, 1.28, 1.29, 1.62, 1.36, 1.42, 1.36, 1.44, and 1.28, respectively. After comparison of fractal dimension, radius of oil droplets captured, and floc length in each oil type, the optimal flocculation temperature was determined to be 30°C. ^

Water for the Wayuu: Procurement and maximization of a limited resource among indigenous pastoralists on the Guajira Peninsula of northern Colombia

For the Wayuu of the Guajira Peninsula of northern Colombia, water procurement has historically been challenging. The ancestral territory of this indigenous pastoral society is windy and arid, with low rainfall, high temperatures and an absence of perennial rivers or streams. In the past, the Wayuu adapted to these environmental conditions by practicing transhumance during the prolonged dry seasons, digging spring wells and artificial ponds and by following guiding principles for water usage. Since the 1930s, the government has made efforts to build additional wind-powered wells and ponds for a growing native population. Notwithstanding, these water solutions have only partly met the necessities; public water sources are limited or unreliable and few attempts are made to generate safe drinking water. Furthermore, the ubiquitous practice of animal husbandry places added pressure on existing sources; livestock consume more water than the human populations in the areas visited. Rapid assessments in four Wayuu areas on the peninsula were conducted by the author and an interdisciplinary team working for the Cerrejón Foundation for Water in La Guajira from 2010 to 2013. The assessments were part of a larger pilot project to design and implement a sustainability plan for reservoir-based water supply systems in the region. This study brings cultural practices and local knowledge to the forefront as key elements for the success of water works and other development projects carried out in Wayuu territory.

Impact of high pCO2 and warmer temperatures on the process of silica biomineralization in the sponge Mycale grandis

Siliceous sponges have survived pre-historical mass extinction events caused by ocean acidification and recent studies suggest that siliceous sponges will continue to resist predicted increases in ocean acidity. In this study, we monitored silica biomineralization in the Hawaiian sponge Mycale grandis under predicted pCO2 and sea surface temperature scenarios for 2100. Our goal was to determine if spicule biomineralization was enhanced or repressed by ocean acidification and thermal stress by monitoring silica uptake rates during short-term (48 h) experiments and comparing biomineralized tissue ratios before and after a long-term (26 d) experiment. In the short-term experiment, we found that silica uptake rates were not impacted by high pCO2 (1050 µatm), warmer temperatures (27°C), or combined high pCO2 with warmer temperature (1119 µatm; 27°C) treatments. The long-term exposure experiments revealed no effect on survival or growth rates of M. grandis to high pCO2 (1198 µatm), warmer temperatures (25.6°C), or combined high pCO2 with warmer temperature (1225 µatm, 25.7°C) treatments, indicating that M. grandis will continue to prosper under predicted increases in pCO2 and sea surface temperature. However, ash-free dry weight to dry weight ratios, subtylostyle lengths, and silicified weight to dry weight ratios decreased under conditions of high pCO2 and combined pCO2 warmer temperature treatments. Our results show that rising ocean acidity and temperature have marginal negative effects on spicule biomineralization and will not affect sponge survival rates of M. grandis.

Fertilisation and larval development in an Antarctic bivalve, Laternula elliptica, under reduced pH and elevated temperatures

Elevated temperatures associated with ocean warming and acidification can influence development and, ultimately, success of larval molluscs. The effect of projected oceanic changes on fertilisation and larval development in an Antarctic bivalve, Laternula elliptica, was investigated through successive larval stages at ambient temperature and pH conditions (-1.6°C and pH 7.98) and conditions representative of projections through to 2100 (-0.5°C to +0.4°C and pH 7.80 to pH 7.65). Where significant effects were detected, increased temperature had a consistently positive influence on larval development, regardless of pH level, while effects of reduced pH varied with larval stage and incubation temperature. Fertilisation was high and largely independent of stressors, with no loss of gamete viability. Mortality was unaffected at all development stages under experimental conditions. Elevated temperatures reduced occurrences of abnormalities in D-larvae and accelerated larval development through late veliger and D-larval stages, with D-larvae occurring 5 d sooner at 0.4°C compared to ambient temperature. Reduced pH did not affect occurrences of abnormalities in larvae, but it slowed the development of calcifying stages. More work is required to investigate the effects of developmental delays of the magnitude seen here in order to better determine the ecological relevance of these changes on longer term larval and juvenile success.

Physical oceanography from 120 CTDs, 79 water bottles stations, and 30 helicopter-borne CTDs during POLARSTERN cruise ANT-XXII/2 (ISPOL)

The Ice Station POLarstern (ISPOL) cruise revisited the western Weddell Sea in late 2004 and obtained a comprehensive set of conductivity-temperature-depth (CTD) data. This study describes the thermohaline structure and diapycnal mixing environment observed in 2004 and compares them with conditions observed more than a decade earlier. Hydrographic conditions on the central western Weddell Sea continental slope, off Larsen C Ice Shelf, in late winter/early spring of 2004/2005 can be described as a well-stratified environment with upper layers evidencing relict structures from intense winter near-surface vertical fluxes, an intermediate depth temperature maximum, and a cold near-bottom layer marked by patchy property distributions. A well-developed surface mixed layer, isolated from the underlying Warm Deep Water (WDW) by a pronounced pycnocline and characterized by lack of warming and by minimal sea-ice basal melting, supports the assumption that upper ocean winter conditions persisted during most of the ISPOL experiment. Much of the western Weddell Sea water column has remained essentially unchanged since 1992; however, significant differences were observed in two of the regional water masses. The first, Modified Weddell Deep Water (MWDW), comprises the permanent pycnocline and was less saline than a decade earlier, whereas Weddell Sea Bottom Water (WSBW) was horizontally patchier and colder. Near-bottom temperatures observed in 2004 were the coldest on record for the western Weddell Sea over the continental slope. Minimum temperatures were ~0.4 and ~0.3 °C colder than during 1992-1993, respectively. The 2004 near-bottom temperature/salinity characteristics revealed the presence of two different WSBW types, whereby a warm, fresh layer overlays a colder, saltier layer (both formed in the western Weddell Sea). The deeper layer may have formed locally as high salinity shelf water (HSSW) that flowed intermittently down the continental slope, which is consistent with the observed horizontal patchiness. The latter can be associated with the near-bottom variability found in Powell Basin with consequences for the deep water outflow from the Weddell Sea.

Estimation of sea surface temperatures and salinity of ODP Site 177-1089 (Appendix A)

ODP Site 1089 is optimally located in order to monitor the occurrence of maxima in Agulhas heat and salt spillage from the Indian to the Atlantic Ocean. Radiolarian-based paleotemperature transfer functions allowed to reconstruct the climatic history for the last 450 kyr at this location. A warm sea surface temperature anomaly during Marine Isotope Stage (MIS) 10 was recognized and traced to other oceanic records along the surface branch of the global thermohaline (THC) circulation system, and is particularly marked at locations where a strong interaction between oceanic and atmospheric overturning cells and fronts occurs. This anomaly is absent in the Vostok ice core deuterium, and in oceanic records from the Antarctic Zone. However, it is present in the deuterium excess record from the Vostok ice core, interpreted as reflecting the temperature at the moisture source site for the snow precipitated at Vostok Station. As atmospheric models predict a subtropical Indian source for such moisture, this provides the necessary teleconnection between East Antarctica and ODP Site 1089, as the subtropical Indian is also the source area of the Agulhas Current, the main climate agent at our study location. The presence of the MIS 10 anomaly in the delta13C foraminiferal records from the same core supports its connection to oceanic mechanisms, linking stronger Agulhas spillover intensity to increased productivity in the study area. We suggest, in analogy to modern oceanographic observations, this to be a consequence of a shallow nutricline, induced by eddy mixing and baroclinic tide generation, which are in turn connected to the flow geometry, and intensity, of the Agulhas Current as it flows past the Agulhas Bank. We interpret the intensified inflow of Agulhas Current to the South Atlantic as responding to the switch between lower and higher amplitude in the insolation forcing in the Agulhas Current source area. This would result in higher SSTs in the Cape Basin during the glacial MIS 10, due to the release into the South Atlantic of the heat previously accumulating in the subtropical and equatorial Indian and Pacific Ocean. If our explanation for the MIS 10 anomaly in terms of an insolation variability switch is correct, we might expect that a future Agulhas SSST anomaly event will further delay the onset of next glacial age. In fact, the insolation forcing conditions for the Holocene (the current interglacial) are very similar to those present during MIS 11 (the interglacial preceding MIS 10), as both periods are characterized by a low insolation variability for the Agulhas Current source area. Natural climatic variability will force the Earth system in the same direction as the anthropogenic global warming trend, and will thus lead to even warmer than expected global temperatures in the near future.

Planktonic foraminiferal d18O and d13C values, derived sea-surface temperatures from d18O and selected planktonic foraminiferal species for core P69 of Hawke Bay off eastern North Island

Recent evidence suggests that the Subtropical Convergence (STC) zone east of New Zealand shifted little from its modern position along Chatham Rise during the last glaciation, and that offshore surface waters north of the STC zone cooled only slightly. However, at nearshore core site P69 (2195 m depth), 115 km off the east coast of North Island and ca 300 km north of the modern STC zone, planktonic foraminiferal species, transfer function data and stable oxygen and carbon isotope records suggest that surface waters were colder by up to 6°C during the late last glacial period compared to the Holocene, and included a strong upwelling signature. Presently site P69 is bathed by south-flowing subtropical waters in the East Cape Current. The nearshore western end of Chatham Rise supports a major bathymetric depression, the Mernoo Saddle, through which some exchange between northern subtropical and southern subantarctic water presently occurs. It is proposed that as a result of much intensified current flows south of the Rise during the last glaciation, a consequence of more compressed subantarctic water masses, lowered sea level, and an expanded and stronger Westerly Wind system, there was accelerated leakage northwards of both Australasian Subantarctic Water and upwelled Antarctic Intermediate Water over Mernoo Saddle in a modified and intensified Southland Current. The expanded cold water masses displaced the south-flowing warm East Cape Current off southeastern North Island, and offshore divergence was accompanied by wind-assisted upwelling of nutrient-rich waters in the vicinity of P69. A comparable kind of inshore cold water jetting possibly characterised most glacial periods since the latest Miocene, and may account for the occasional occurrence of subantarctic marine fossils in onland late Cenozoic deposits north of the STC zone, rather than invoking wholesale major oscillations of the oceanic STC itself.

R-codes, and coral abundance, water temperature and transect characteristics of nearshore reefs in Belize

Coral reefs are increasingly threatened by global and local anthropogenic stressors, such as rising seawater temperature and nutrient enrichment. These two stressors vary widely across the reef face and parsing out their influence on coral communities at reef system scales has been particularly challenging. Here, we investigate the influence of temperature and nutrients on coral community traits and life history strategies on lagoonal reefs across the Belize Mesoamerican Barrier Reef System (MBRS). A novel metric was developed using ultra-high-resolution sea surface temperatures (SST) to classify reefs as enduring low (lowTP), moderate (modTP), or extreme (extTP) temperature parameters over 10 years (2003 to 2012). Chlorophyll-a (chl a) records obtained for the same interval were employed as a proxy for bulk nutrients and these records were complemented with in situ measurements to "sea truth" nutrient content across the three reef types. Chl a concentrations were highest at extTP sites, medial at modTP sites and lowest at lowTP sites. Coral species richness, abundance, diversity, density, and percent cover were lower at extTP sites compared to lowTP and modTP sites, but these reef community traits did not differ between lowTP and modTP sites. Coral life history strategy analyses showed that extTP sites were dominated by hardy stress-tolerant and fast-growing weedy coral species, while lowTP and modTP sites consisted of competitive, generalist, weedy, and stress-tolerant coral species. These results suggest that differences in coral community traits and life history strategies between extTP and lowTP/modTP sites were driven primarily by temperature differences with differences in nutrients across site types playing a lesser role. Dominance of weedy and stress-tolerant genera at extTP sites suggests that corals utilizing these two life history strategies may be better suited to cope with warmer oceans and thus may warrant further protective status during this climate change interval. Data associated with this project are archived here, including: -SST data -Satellite Chl a data -Nutrient measurements -Raw coral community survey data For questions contact Justin Baumann (j.baumann3 gmail.com)