Bulk sediment parameter of three sediment cores from permafrost lowlands, Alaska Arctic Coastal Plain

Arctic lowland landscapes have been modified by thermokarst lake processes throughout the Holocene. Thermokarst lakes form as a result of ice-rich permafrost degradation and they may expand over time through thermal and mechanical shoreline erosion. We studied proximal and distal sedimentary records from a thermokarst lake located on the Arctic Coastal Plain of northern Alaska to reconstruct the impact of catchment dynamics and morphology on the lacustrine depositional environment and to quantify carbon accumulation in thermokarst lake sediments. Short cores were collected for analysis of pollen, sedimentological and geochemical proxies. Radiocarbon and Pb/Cs dating, as well as extrapolation of measured historic lake expansion rates, were applied to estimate a minimum lake age of ~ 1,400 calendar years BP. The pollen record is in agreement with the young lake age as it does not include evidence of the "alder high" that occurred in the region ~ 4.0 cal ka BP. The lake most likely initiated from a remnant pond in a drained thermokarst lake basin (DTLB) and deepened rapidly as evidenced by accumulation of laminated sediments. Increasing oxygenation of the water column as shown by higher Fe/Ti and Fe/S ratios in the sediment indicate shifts in ice regime with increasing water depth. More recently, the sediment source changed as the thermokarst lake expanded through lateral permafrost degradation, alternating from redeposited DTLB sediments, to increased amounts of sediment from eroding, older upland deposits, followed by a more balanced combination of both DTLB and upland sources. The characterizing shifts in sediment sources and depositional regimes in expanding thermokarst lakes were therefore archived in the thermokarst lake sedimentary record. This study also highlights the potential for Arctic lakes to recycle old carbon from thawing permafrost and thermokarst processes.

A tight-binding analysis of the electronic properties of III-nitride semiconductors

This thesis divides into two distinct parts, both of which are underpinned by the tight-binding model. The first part covers our implementation of the tight-binding model in conjunction with the Berry phase theory of electronic polarisation to probe the atomistic origins of spontaneous polarisation and piezoelectricity as well as attempting to accurately calculate the values and coefficients associated with these phenomena. We first develop an analytic model for the polarisation of a one-dimensional linear chain of atoms. We compare the zincblende and ideal wurtzite structures in terms of effective charges, spontaneous polarisation and piezoelectric coefficients, within a first nearest neighbour tight-binding model. We further compare these to real wurtzite structures and conclude that accurate quantitative results are beyond the scope of this model but qualitative trends can still be described. The second part of this thesis deals with implementing the tight-binding model to investigate the effect of local alloy fluctuations in bulk AlGaN alloys and InGaN quantum wells. We calculate the band gap evolution of Al1_xGaxN across the full composition range and compare it to experiment as well as fitting bowing parameters to the band gap as well as to the conduction band and valence band edges. We also investigate the wavefunction character of the valence band edge to determine the composition at which the optical polarisation switches in Al1_xGaxN alloys. Finally, we examine electron and hole localisation in InGaN quantum wells. We show how the built-in field localises the carriers along the c-axis and how local alloy fluctuations strongly localise the highest hole states in the c-plane, while the electrons remain delocalised in the c-plane. We show how this localisation affects the charge density overlap and also investigate the effect of well width fluctuations on the localisation of the electrons.

14C specific radiocarbon ages and bulk ages accompanied by geochemical proxys from surface sediment samples in the Black Sea

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.

Geochemical analysis of surface sediments from the ocean floor and from sea ice in the northern Atlantic and Arctic Oceans

Barium in marine terrigenous surface sediments of the European Nordic Seas is analysed to evaluate its potential as palaeoproductivity proxy. Biogenic Ba is calculated from Ba and Al data using a conventional approach. For the determination of appropriate detrital Ba/Al ratios a compilation of Ba and Al analyses in rocks and soils of the catchments surrounding the Nordic Seas is presented. The resulting average detrital Ba/Al ratio of 0.0070 is similar to global crustal average values. In the southern Nordic Seas the high input of basaltic material with a low Ba/Al ratio is evident from high values of magnetic susceptibility and low Al/Ti ratios. Most of the Ba in the marine surface sediments is of terrigenous and not of biogenic origin. Variability in the lithogenic composition has been considered by the application of regionally varying Ba/Al ratios. The biogenic Ba values are comparable with those observed in the central Arctic Ocean, they are lower than in other oceanic regions. Biogenic Ba values are correlated with other productivity proxies and with oceanographic data for a validation of the applicability in paleoceanography. In the Iceland Sea and partly in the marginal sea-ice zone of the Greenland Sea elevated values of biogenic Ba indicate seasonal phytoplankton blooms. In both areas paleoproductivities may be reconstructed based on Ba and Al data of sediment cores.

Heavy mineral and bulk mineral compositions of cores from Kumano Basin

Coring during Integrated Ocean Drilling Program Expeditions 315, 316, and 333 recovered turbiditic sands from the forearc Kumano Basin (Site C0002), a Quaternary slope basin (Site C0018), and uplifted trench wedge (Site C0006) along the Kumano Transect of the Nankai Trough accretionary wedge offshore of southwest Japan. The compositions of the submarine turbiditic sands here are investigated in terms of bulk and heavy mineral modal compositions to identify their provenance and dispersal mechanisms, as they may reflect changes in regional tectonics during the past ca. 1.5 Myrs. The results show a marked change in the detrital signature and heavy mineral composition in the forearc and slope basin facies around 1 Ma. This sudden change is interpreted to reflect a major change in the sand provenance, rather than heavy mineral dissolution and/or diagenetic effects, in response to changing tectonics and sedimentation patterns. In the trench-slope basin, the sands older than 1 Ma were probably eroded from the exposed Cretaceous-Tertiary accretionary complex of the Shimanto Belt and transported via the former course of the Tenryu submarine canyon system, which today enters the Nankai Trough northeast of the study area. In contrast, the high abundance of volcanic lithics and volcanic heavy mineral suites of the sands younger than 1 Ma points to a strong volcanic component of sediment derived from the Izu-Honshu collision zones and probably funnelled to this site through the Suruga Canyon. However, sands in the forearc basin show persistent presence of blue sodic amphiboles across the 1 Ma boundary, indicating continuous flux of sediments from the Kumano/Kinokawa River. This implies that the sands in the older turbidites were transported by transverse flow down the slope. The slope basin facies then switched to reflect longitudinal flow around 1 Ma, when the turbiditic sand tapped a volcanic provenance in the Izu-Honshu collision zone, while the sediments transported transversely became confined in the Kumano Basin. Therefore, the change in the depositional systems around 1 Ma is a manifestation of the decoupling of the sediment routing pattern from transverse to long-distance axial flow in response to forearc high uplift along the megasplay fault.

Element concentrations of bulk sediment from the Southern Cape Basin

High-resolution records of Ca and Sr were obtained from shipboard XRF analyses of bulk sediments in five gravity cores from the southern Cape Basin, South Atlantic Ocean. Sr/Ca ratios display regular glacial/interglacial variations of 14-40% and reveal a close correlation with the SPECMAP record, minimum Sr/Ca ratios appearing during glacial (delta18 O) maxima, distinct increases during periods of deglaciation, and highest ratios in interstadials. Shifts in carbonate-producing phytoplankton and/or zooplankton assemblages over glacial/interglacial cycles are suggested to be the main cause for the observed variations in Sr/Ca patterns. Quick assessment of the relationship between Sr/Ca ratios and the SPECMAP record made it possible to easily transfer an age model to the newly collected cores already during the cruise.

Sedimentological analysis of eight cores from the Amundsen Sea

Recent palaeoglaciological studies on the West Antarctic shelf have mainly focused on the wide embayments of the Ross and Amundsen seas in order to reconstruct the extent and subsequent retreat of the West Antarctic Ice Sheet (WAIS) since the Last Glacial Maximum (LGM). However, the narrower shelf sectors between these two major embayments have remained largely unstudied in previous geological investigations despite them covering extensive areas of the West Antarctic shelf. Here, we present the first systematic marine geological and geophysical survey of a shelf sector offshore from the Hobbs Coast. It is dominated by a large grounding zone wedge (GZW), which fills the base of a palaeo-ice stream trough on the inner shelf and marks a phase of stabilization of the grounding line during general WAIS retreat following the last maximum ice-sheet extent in this particular area (referred to as the Local Last Glacial Maximum, 'LLGM'). Reliable age determination on calcareous microfossils from the infill of a subglacial meltwater channel eroded into the GZW reveals that grounded ice had retreated landward of the GZW before ~20.88 cal. ka BP, with deglaciation of the innermost shelf occurring prior to ~12.97 cal. ka BP. Geophysical sub-bottom information from the inner-, mid- and outer shelf indicates grounded ice extended to the shelf edge prior to the formation of the GZW. Assuming the wedge was deposited during deglaciation, we infer the timing of maximum grounded ice extent occurred before ~20.88 cal. ka BP. This could suggest that the WAIS retreat from the outer shelf was already underway during or even prior to the global LGM (~23-19 cal. ka BP). Our new findings give insights into the regional deglacial behaviour of this understudied part of the West Antarctic shelf and at the same time support early deglaciation ages recently presented for adjacent drainage sectors of the WAIS. If correct, these findings contrast with the hypothesis that initial deglaciation of Antarctic Ice Sheets occurred synchronously at ~19 cal. ka BP.

Core scans and lithologic analysis of Subglacial Lake Whillans sediment cores

The hydrologic system beneath the Antarctic Ice Sheet is thought to influence both the dynamics and distribution of fast flowing ice streams, which discharge most of the ice lost by the ice sheet. Despite considerable interest in understanding this subglacial network and its affect on ice flow, in situ observations from the ice sheet bed are exceedingly rare. Here we describe the first sediment cores recovered from an active subglacial lake. The lake, known as Subglacial Lake Whillans, is part of a broader, dynamic hydrologic network beneath the Whillans Ice Stream in West Antarctica. Even though "floods" pass through the lake, the lake floor shows no evidence of erosion or deposition by flowing water. By inference, these floods must have insufficient energy to erode or transport significant volumes of sediment coarser than silt. Consequently, water flow beneath the region is probably incapable of incising continuous channels into the bed and instead follows preexisting subglacial topography and surface slope. Sediment on the lake floor consists of till deposited during intermittent grounding of the ice stream following flood events. The fabrics within the till are weaker than those thought to develop in thick deforming beds suggesting subglacial sediment fluxes across the ice plain are currently low and unlikely to have a large stabilizing effect on the ice stream's grounding zone.

Annotated record and chemical analysis of manganese nodules from R/V Moana Wave Cruise Mn-74-01 and Mn-74-02 stations

Cruise Mn-74-02 of the R/V MOANA WAVE was the second part of the field work of the NSF/IDOE Inter-University Ferromanganese Research Program in 1974, and we gratefully acknowledge the support of the office for the International Decade of Ocean Exploration and the Office of Oceanographic Facilities and Support. This program was designed to investigate the origin, growth, and distribution of copper/nickel-rich manganese nodules in the Pacific Ocean. The field effort was designed to satisfy sample requirements of the fifteen principal investigators, while increasing general knowledge of the copper/nickel-rich nodule deposits of the equatorial Pacific. This report is the second of a series of cruise reports designed to assist sample requests for documented nodules, sediment, and water samples so that laboratory results can be realistically compared and related to the environment of nodule growth. Nodule samples and bathymetric and navigational data are archived at the Hawaii Institute of Geophysics, University of Hawaii. Bulk chemical analyses of nodules and reduction of survey data were carried out at Hawaii. Sediment cores were stored at the University of Hawaii and at Scripps Institution of Oceanography. The SIO analytical facility provided stratigraphic data on sediment chemistry.

Analysis of the moisture effect on the mechanical behaviour of an adhesively bonded joint under proportional multi-axial loads

The objective of the study is to identify the 3D behaviour of an adhesive in an assembly, and to take into account the effect of ageing in a marine environment. To that end, three different tests were employed. Gravimetric analyses were used to determine the water diffusion kinetics in the adhesive. Bulk tensile tests were performed to highlight the effects of humid ageing on the adhesive behaviour. Modified Arcan tests were performed for several ageing times to obtain the experimental database which was necessary to identify constitutive models. A Mahnken-Schlimmer type model was determined for the unaged state according to a procedure developed in a previous study. This identification used inverse techniques. It was based on the unaged modified Arcan results and on a coupling between an optimisation routine and finite-element analysis. Then, a global inverse identification procedure was developed. Its aim was to relate the unaged parameters to the moisture concentration and overcome the difficulties usually associated with ageing of bonded assemblies in a humid environment: a non-uniformity of the stress state and a gradient of mechanical properties in the adhesive. This procedure was similar to the one used in the first part but needed modified Arcan results for several ageing times. It also required an initial assumption for the evolution of the Mahnken-Schlimmer parameters with the moisture concentration.

Activity-based life cycle costing model for cost estimation and monitoring – Case: manned and autonomous dry bulk carrier

Recent developments in automation, robotics and artificial intelligence have given a push to a wider usage of these technologies in recent years, and nowadays, driverless transport systems are already state-of-the-art on certain legs of transportation. This has given a push for the maritime industry to join the advancement. The case organisation, AAWA initiative, is a joint industry-academia research consortium with the objective of developing readiness for the first commercial autonomous solutions, exploiting state-of-the-art autonomous and remote technology. The initiative develops both autonomous and remote operation technology for navigation, machinery, and all on-board operating systems. The aim of this study is to develop a model with which to estimate and forecast the operational costs, and thus enable comparisons between manned and autonomous cargo vessels. The building process of the model is also described and discussed. Furthermore, the model’s aim is to track and identify the critical success factors of the chosen ship design, and to enable monitoring and tracking of the incurred operational costs as the life cycle of the vessel progresses. The study adopts the constructive research approach, as the aim is to develop a construct to meet the needs of a case organisation. Data has been collected through discussions and meeting with consortium members and researchers, as well as through written and internal communications material. The model itself is built using activity-based life cycle costing, which enables both realistic cost estimation and forecasting, as well as the identification of critical success factors due to the process-orientation adopted from activity-based costing and the statistical nature of Monte Carlo simulation techniques. As the model was able to meet the multiple aims set for it, and the case organisation was satisfied with it, it could be argued that activity-based life cycle costing is the method with which to conduct cost estimation and forecasting in the case of autonomous cargo vessels. The model was able to perform the cost analysis and forecasting, as well as to trace the critical success factors. Later on, it also enabled, albeit hypothetically, monitoring and tracking of the incurred costs. By collecting costs this way, it was argued that the activity-based LCC model is able facilitate learning from and continuous improvement of the autonomous vessel. As with the building process of the model, an individual approach was chosen, while still using the implementation and model building steps presented in existing literature. This was due to two factors: the nature of the model and – perhaps even more importantly – the nature of the case organisation. Furthermore, the loosely organised network structure means that knowing the case organisation and its aims is of great importance when conducting a constructive research.

Preventing encrypted traffic analysis

Many existing encrypted Internet protocols leak information through packet sizes and timing. Though seemingly innocuous, prior work has shown that such leakage can be used to recover part or all of the plaintext being encrypted. The prevalence of encrypted protocols as the underpinning of such critical services as e-commerce, remote login, and anonymity networks and the increasing feasibility of attacks on these services represent a considerable risk to communications security. Existing mechanisms for preventing traffic analysis focus on re-routing and padding. These prevention techniques have considerable resource and overhead requirements. Furthermore, padding is easily detectable and, in some cases, can introduce its own vulnerabilities. To address these shortcomings, we propose embedding real traffic in synthetically generated encrypted cover traffic. Novel to our approach is our use of realistic network protocol behavior models to generate cover traffic. The observable traffic we generate also has the benefit of being indistinguishable from other real encrypted traffic further thwarting an adversary's ability to target attacks. In this dissertation, we introduce the design of a proxy system called TrafficMimic that implements realistic cover traffic tunneling and can be used alone or integrated with the Tor anonymity system. We describe the cover traffic generation process including the subtleties of implementing a secure traffic generator. We show that TrafficMimic cover traffic can fool a complex protocol classification attack with 91% of the accuracy of real traffic. TrafficMimic cover traffic is also not detected by a binary classification attack specifically designed to detect TrafficMimic. We evaluate the performance of tunneling with independent cover traffic models and find that they are comparable, and, in some cases, more efficient than generic constant-rate defenses. We then use simulation and analytic modeling to understand the performance of cover traffic tunneling more deeply. We find that we can take measurements from real or simulated traffic with no tunneling and use them to estimate parameters for an accurate analytic model of the performance impact of cover traffic tunneling. Once validated, we use this model to better understand how delay, bandwidth, tunnel slowdown, and stability affect cover traffic tunneling. Finally, we take the insights from our simulation study and develop several biasing techniques that we can use to match the cover traffic to the real traffic while simultaneously bounding external information leakage. We study these bias methods using simulation and evaluate their security using a Bayesian inference attack. We find that we can safely improve performance with biasing while preventing both traffic analysis and defense detection attacks. We then apply these biasing methods to the real TrafficMimic implementation and evaluate it on the Internet. We find that biasing can provide 3-5x improvement in bandwidth for bulk transfers and 2.5-9.5x speedup for Web browsing over tunneling without biasing.

Characterization of Copper Covetic Bulk and Films: Copper with High Carbon Content

Incorporation of carbon nanostructures in metals is desirable to combine the strongly bonded electrons in the metal and the free electrons in carbon nanostructures that give rise to high ampacity and high conductivity, respectively. Carbon in copper has the potential to impact industries such as: building construction, power generation and transmission, and microelectronics. This thesis focuses on the structure and properties of bulk and thin films of a new material, Cu covetic, that contains carbon in concentrations up to 16 at.%. X-ray photoelectron spectroscopy (XPS) shows C 1s peak with both sp2 and sp3 bonded C measuring up to 3.5 wt.% (16 at.%). High resolution transmission electron microscopy and electron diffraction of bulk covetic samples show a modulated structure of ≈ 1.6 nm along several crystallographic directions in regions that have high C content suggesting that the carbon incorporates into the copper lattice forming a network. Electron energy loss spectra (EELS) from covetics reveal that the level of graphitization from the source material, activated carbon, is maintained in the covetic structure. Bulk Cu covetics have a slight increase in the lattice constant, as well as <111> texturing, or possibly a different structure, compared to pure Cu. Density functional theory calculations predict bonding between C and Cu at the edges and defects of graphene sheets. The electrical resistivity of bulk covetics first increases and then decreases with increasing C content. Cu covetic films were deposited using e-beam and pulsed laser deposition (PLD) at different temperatures. No copper oxide or any allotropes of carbon are present in the films. The e-beam films show enhanced electrical and optical properties when compared to pure Cu films of the same thickness even though no carbon was detected by XPS or EELS. They also have slightly higher ampacity than Cu metal films. EELS analysis of the C-K-edge in the PLD films indicate that graphitic carbon is transferred from the bulk into the films with uniform carbon distribution. PLD films exhibit flatter and higher transmittance curves and sheet resistance two orders of magnitude lower than e-beam films leading to a high figure of merit as transparent conductors.