Magnetic extracts of three gravity cores located at the Ceará Rise, the Mid-Atlantic Ridge and the Sierra Leone Rise

The magnetic microparticle and nanoparticle inventories of marine sediments from equatorial Atlantic sites were investigated by scanning and transmission electron microscopy to classify all present detrital and authigenic magnetic mineral species and to investigate their regional distribution, origin, transport, and preservation. This information is used to establish source-to-sink relations and to constrain environmental magnetic proxy interpretations for this area. Magnetic extracts were prepared from sediments of three supralysoclinal open ocean gravity cores located at the Ceará Rise (GeoB 1523-1; 3°49.9'N/41°37.3'W), the Mid-Atlantic Ridge (GeoB 4313-2; 4°02.8'N/33°26.3'W), and the Sierra Leone Rise (GeoB 2910-1; 4°50.7'N/21°03.2'W). Sediments from two depths corresponding to marine isotope stages 4 and 5.5 were processed. This selection represents glacial and interglacial conditions of sedimentation for the western, central, and eastern equatorial Atlantic and avoids interferences from subsurface and anoxic processes. Crystallographic, elemental, morphological, and granulometric data of more than 2000 magnetic particles were collected by scanning and transmission electron microscopy. On basis of these properties, nine particle classes could be defined: detrital magnetite, titanomagnetite (fragmental and euhedral), titanomagnetite-hemoilmentite intergrowths, silicates with magnetic inclusions, microcrystalline hematite, magnetite spherules, bacterial magnetite, goethite needles, and nanoparticle clusters. Each class can be associated with fluvial, eolian, subaeric, and submarine volcanic, biogenic, or chemogenic sources. Large-scale sedimentation patterns are delineated as well: detrital magnetite is typical of Amazon discharge, fragmental titanomagnetite is a submarine weathering product of mid-ocean ridge basalts, and titanomagnetite-hemoilmenite intergrowths are common magnetic particles in West African dust. This clear regionalization underlines that magnetic petrology is an excellent indicator of source-to-sink relations. Hematite encrustations, magnetic spherules, and nanoparticle clusters were found at all investigated sites, while bacterial magnetite and authigenic hematite were only detected at the more oxic western site. At the eastern site, surface pits and crevices were seen on the crystal faces indicating subtle early diagenetic reductive dissolution. It was observed that paleoclimatic signatures of magnetogranulometric parameters such as the ratio of anhysteretic and isothermal remanent magnetizations can be formed either by mixing of multiple sources with separate, relatively narrow grain size ranges (western site) or by variable sorting of a single source with a broad grain size distribution (eastern site). Hematite, goethite, and possibly ferrihydrite nanoparticles occur in all sediment cores studied and have either high-coercive or superparamagnetic properties depending on their partly ultrafine grain sizes. These two magnetic fractions are generally discussed as separate fractions, but we suggest that they could actually be genetically linked.

Geochemical analysis at ODP Site 207-1261 from the Demerara Rise in the western equatorial Atlantic

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (~15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ~15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ?90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ~15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS**- production.

Development of an instrument measuring the quality of residential care facilities for older people

Aims. To validate the Swedish version of the Sheffield Care Environment Assessment Matrix (S-SCEAM). The instrument’s items measure environmental elements important for supporting the needs of older people, and conceptualized within eight domains. Methods. Item relevance was assessed by a group of experts and measured using content validity index (CVI). Test-retest and inter-rater reliability tests were performed.  The domain structure was assessed by the inter-rater agreement of a second group of experts, and measured using Fleiss kappa. Results. All items attained a CVI above 0.78, the suggested criteria for excellent content validity. Test-retest reliability showed high stability (96% and 95% for two independent raters respectively), and inter-rater reliability demonstrated high levels of agreement (95% and 94% on two separate rating occasions). Kappa values were very good for test-retest (κ = 0.903 and 0.869) and inter-rater reliability (κ = 0.851 and 0.832). Domain structure was good,  Fleiss’ kappa was 0.63 (range 0.45 to 0.75).    Conclusion. The S-SCEAM of 210 items and eight domains showed good content validity and construct validity. The instrument is suggested for use in measuring of the quality of the physical environment in residential care facilities for older persons.

Air Pollution and High Density Lipoprotein Structure and Function

Thesis (Ph.D.)--University of Washington, 2016-06

Coupled Ge/Si and Ge isotope ratios as geochemical tracers of seafloor hydrothermal systems: Case studies at Loihi Seamount and East Pacific Rise 9°50’N

Germanium (Ge) and Silicon (Si) exhibit similar geochemical behaviour in marine environments but are variably enriched in seafloor hydrothermal fluids relative to seawater. In this study, Ge isotope and Ge/Si ratio systematics were investigated in low temperature hydrothermal vents from Loihi Seamount (Pacific Ocean, 18°54’N, 155°15’W) and results were compared to high-temperature vents from the East Pacific Rise (EPR) at 9°50’N. Loihi offers the opportunity to understand contrasting Ge and Si behaviour in low temperature seafloor hydrothermal systems characterized by abundant Fe oxyhydroxide deposition at the seafloor. The results show that both Ge/Si and δ74/70Ge in hydrothermal fluids are fractionated relative to the basaltic host rocks. The enrichment in Ge vs. Si relative to fresh basalts, together with Ge isotope fractionation (Δ74/70Ge fluid-basalt up to 1.15 ‰ at EPR 9°50’N and 1.64 ‰ at Loihi) are best explained by the precipitation of minerals (e.g. quartz and Fe-sulfides) during higher temperature seawater-rock reactions in the subsurface. The study of Fe-rich hydrothermal deposits at Loihi, largely composed of Fe-oxyhydroxides, shows that Ge isotopes are also fractionated upon mineral precipitation at the seafloor. We obtained an average Ge isotope fractionation factor between Fe-oxyhydroxide (ferrihydrite) and dissolved Ge in the fluid of -2.0 ± 0.6 ‰ (2sd), and a maximum value of -3.6 ± 0.6 ‰ (2sd), which is consistent with recent theoretical and experimental studies. The study of a hydrothermal chimney at Bio 9 vent at EPR 9°50’N also demonstrates that Ge isotopes are fractionated by approximately -5.6 ± 0.6 ‰ (2sd) during precipitation of metal sulfides under hydrothermal conditions. Using combined Ge/Si and estimated Ge isotope signatures of Ge sinks and sources in seawater, we propose a preliminary oceanic budget of Ge which reveals that an important sink, referred as the “missing Ge sink”, may correspond to Ge sequestration into authigenic Fe-oxyhydroxides in marine sediments. This study shows that combining Ge/Si and δ74/70Ge systematics provides a useful tool to trace hydrothermal Ge and Si sources in marine environments and to understand formation processes of seafloor hydrothermal deposits.

Impact of using solar heat pumps for domestic hot water in Portuguese residential buildings

In recent years, we have seen an improvement of existing facilities in dwellings in Portugal. Within the heat pumps systems, there is a special type known as direct expansion heat pump assisted by Solar Collector (DX-SAHP). It was calculate the SPF indicator for 30 regions of Portugal. It was analyses the potential of reductions of CO2 and primary energy use for the retrofitting of DHW preparation systems. It was found that the performances of this type of equipment are benefiting from the Portuguese climate conditions, especially in the South and in the Autonomous Regions. Best SPF was obtained for Beja. It was found in all regions of the high potential for reducing CO2 emissions and verifying a potential significant reduction of primary energy consumption.

Ecology, physiology and performance in high-rate anaerobic digestion

The design demands on water and sanitation engineers are rapidly changing. The global population is set to rise from 7 billion to 10 billion by 2083. Urbanisation in developing regions is increasing at such a rate that a predicted 56% of the global population will live in an urban setting by 2025. Compounding these problems, the global water and energy crises are impacting the Global North and South alike. High-rate anaerobic digestion offers a low-cost, low-energy treatment alternative to the energy intensive aerobic technologies used today. Widespread implementation however is hindered by the lack of capacity to engineer high-rate anaerobic digestion for the treatment of complex wastes such as sewage. This thesis utilises the Expanded Granular Sludge Bed bioreactor (EGSB) as a model system in which to study the ecology, physiology and performance of high-rate anaerobic digestion of complex wastes. The impacts of a range of engineered parameters including reactor geometry, wastewater type, operating temperature and organic loading rate are systematically investigated using lab-scale EGSB bioreactors. Next generation sequencing of 16S amplicons is utilised as a means of monitoring microbial ecology. Microbial community physiology is monitored by means of specific methanogenic activity testing and a range of physical and chemical methods are applied to assess reactor performance. Finally, the limit state approach is trialled as a method for testing the EGSB and is proposed as a standard method for biotechnology testing enabling improved process control at full-scale. The arising data is assessed both qualitatively and quantitatively. Lab-scale reactor design is demonstrated to significantly influence the spatial distribution of the underlying ecology and community physiology in lab-scale reactors, a vital finding for both researchers and full-scale plant operators responsible for monitoring EGSB reactors. Recurrent trends in the data indicate that hydrogenotrophic methanogenesis dominates in high-rate anaerobic digestion at both full- and lab-scale when subject to engineered or operational stresses including low-temperature and variable feeding regimes. This is of relevance for those seeking to define new directions in fundamental understanding of syntrophic and competitive relations in methanogenic communities and also to design engineers in determining operating parameters for full-scale digesters. The adoption of the limit state approach enabled identification of biological indicators providing early warning of failure under high-solids loading, a vital insight for those currently working empirically towards the development of new biotechnologies at lab-scale.

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.

The Relation between Substance Use and Medication Adherence among HIV Positive Substance Users in Residential Treatment

Poor medication adherence is problematic among HIV positive, low-income African-American substance users. Substance use has been shown to be associated with poor medication adherence, though we do not know the mechanism that underlies this relationship. Lack of positive environmental rewards and the propensity to discount delayed rewards may be possible mechanisms to explain this relationship. Using baseline data from a randomized controlled trial, we examined the relationships between substance use and medication adherence, testing both environmental rewards and delay discounting as independent mediators. There was a main effect of substance use on adherence, such that high frequency of substance use predicted poor adherence. There was also a main effect of environmental rewards on adherence, such that a lack of environmental reinforcement predicted poor adherence. This study shed light on the processes that contribute to low adherence, namely substance use and lack of environmental contingencies, and suggests important targets for intervention.

ESSAYS ON DISPLACED WORKERS AND RESIDENTIAL MIGRATION

In this dissertation, I explore how workers’ human capital, local industry composition, and business cycles affect employment outcomes and residential migration for job losers and other workers. I first examine whether the poor employment outcomes of job losers are due to a lack of jobs that require their human capital within their local labor market. I answer this question by analyzing the extent to which the industry composition in the job loser’s local labor market affects employment outcomes when job loss occurs during expansions and during recessions. I find that if job losers reside in an area with a high employment concentration of their original industry of employment, they are 2.1-2.8 percent more likely to be re-employed at another job if job loss occurs during an expansion; I find an insignificant relationship in most specifications when job loss occurs during a recession, and in some specifications I even find a negative relationship between industry concentration and employment. I conclude that the industry composition within an area matters for job losers, since firms are more willing to hire workers from within their own industry, as these workers have more relevant accumulated human capital. However, firms are less likely to hire during a recession, making job losers’ human capital less important for job finding. Next, Erika McEntarfer, Henry Hyatt, and I examine whether the business cycle affects earnings changes for job losers, and the factors that explain these differences across time. We find that job losers who lost their job during the Great Recession have earnings changes that are 10 percent more negative relative to other job losers from other periods. This result is driven primarily by longer nonemployment lengths and worse subsequent job matches. Finally, Erika McEntarfer, Henry Hyatt, Alexandria Zhang, and I explore the extent to which residential migration is driven by job opportunities. We use four databases and find that changes in job moves explain some of the changes in residential migration, but the relationship is not as strong as previously documented. We find that migration patterns differ across databases, with some databases documenting steeper declines and more cyclicality.

Geochemical analysis at ODP Site 207-1259 from the Demerara Rise in the western equatorial Atlantic

Organic carbon-rich shales deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 were drilled during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic variations in marine and detrital sediment contribution, depositional processes, and bottom water redox conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V, Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites was generally dominated by marine material (carbonate, organic matter, opal) although relationships of detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular, and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older Cenomanian-Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms controlling continental supply and ocean redox state were time-invariant and kept the western equatorial Atlantic margin widely anoxic over millions of years.

Evaluating the Effects of Sea Level Rise on Sea Turtle Nesting Sites: A Case Study of the Archie Carr National Wildlife Refuge

The purpose of this thesis was to determine the extent of sea level rise (SLR) impact on sea turtle nesting beach habitat on Archie Carr National Wildlife Refuge (NWR) as well as impacts on management strategies. The Archie Carr NWR is of exceptional importance due to the high density of Loggerhead, Leatherback, and Green sea turtles that nest there in the summer months. GIS data provided by the Archie Carr NWR and various SLR scenarios, provided by both the Intergovernmental Panel on Climate Change (IPCC) as well as leading scholars, were used to determine inundation area loss across the Refuge as well as nearby parcels targeted for possible acquisition. Inundation losses for the six scenarios were calculated to be in the 20-25% range. Approximately 26% of current lower priority parcels are reclassified as high priority when integrating this information. Therefore, a significant revision to future acquisition strategies is recommended.

Building environmental assessment scheme for residential building in Brunei

Building's construction activities, operation and demolition are increasingly recognised as a major source of environmental impact. One strategy for reducing such impacts is most widely known by the term Building Environmental Assessment (BEA). The research is an attempt to develop a new BEA scheme for residential buildings in Brunei which focussing on identifying BEA indicators that best suit for Brunei environment, social and economy. Studies show that Brunei residential sector needs urgent attention to transform its current consumption rate in more sustainable way. Recent launch of Brunei Green Building Council, mandatory energy efficiency guidelines and declaration of ambitious energy intensity reduction target, a new BEA scheme will help contribute sustainability target in residential sector. However the issues of developing a new BEA schemes using existing methods may face constraints in their effectiveness. In this regard, a consensus-forming technique-Delphi method-helps improve greater communication and gain consensus from experts in the construction industry through series of questionnaires. As a result, the final framework is produced comprises of 7 key categories and 37 applicable criteria that achieved high degree of consensus and importance.

Landscape Patterns of Permafrost Disturbance and Degradation in the Canadian High Arctic

Intensification of permafrost disturbances such as active layer detachments (ALDs) and retrogressive thaw slumps (RTS) have been observed across the circumpolar Arctic. These features are indicators of unstable conditions stemming from recent climate warming and permafrost degradation. In order to understand the processes interacting to give rise to these features, a multidisciplinary approach is required; i.e., interactions between geomorphology, hydrology, vegetation and ground thermal conditions. The goal of this research is to detect and map permafrost disturbance, predict landscape controls over disturbance and determine approaches for monitoring disturbance, all with the goal of contributing to the mitigation of permafrost hazards. Permafrost disturbance inventories were created by applying semi-automatic change detection techniques to IKONOS satellite imagery collected at the Cape Bounty Arctic Watershed Observatory (CBAWO). These methods provide a means to estimate the spatial distribution of permafrost disturbances for a given area for use as an input in susceptibility modelling. Permafrost disturbance susceptibility models were then developed using generalized additive and generalized linear models (GAM, GLM) fitted to disturbed and undisturbed locations and relevant GIS-derived predictor variables (slope, potential solar radiation, elevation). These models successfully delineated areas across the landscape that were susceptible to disturbances locally and regionally when transferred to an independent validation location. Permafrost disturbance susceptibility models are a first-order assessment of landscape susceptibility and are promising for designing land management strategies for remote permafrost regions. Additionally, geomorphic patterns associated with higher susceptibility provide important knowledge about processes associated with the initiation of disturbances. Permafrost degradation was analyzed at the CBAWO using differential interferometric synthetic aperture radar (DInSAR). Active-layer dynamics were interpreted using inter-seasonal and intra-seasonal displacement measurements and highlight the importance of hydroclimatic factors on active layer change. Collectively, these research approaches contribute to permafrost monitoring and the assessment of landscape-scale vulnerability in order to develop permafrost disturbance mitigation strategies.

Climate Change Adaptation Case Study: Benefit-Cost Analysis of Coastal Flooding Hazard Mitigation

The damage Hurricane Sandy caused had far-reaching repercussions up and down the East Coast of the United States. Vast coastal flooding accompanied the storm, inundating homes, businesses, and utility and emergency facilities. Since the storm, projects to mitigate similar future floods have been scrutinized. Such projects not only need to keep out floodwaters but also be designed to withstand the effect that climate change might have on rising sea levels and increased flood risk. In this study, we develop an economic model to assess the costs and benefits of a berm (sea wall) to mitigate the effects of flooding from a large storm. We account for the lifecycle costs of the project, which include those for the upfront construction of the berm, ongoing maintenance, land acquisition, and wetland and recreation zone construction. Benefits of the project include avoided fatalities, avoided residential and commercial damages, avoided utility and municipal damages, recreational and health benefits, avoided debris removal expenses, and avoided loss of function of key transportation and commercial infrastructure located in the area. Our estimate of the beneficial effects of the berm includes ecosystem services from wetlands and health benefits to the surrounding community from a park and nature system constructed along the berm. To account for the effects of climate change and verify that the project will maintain its effectiveness over the long term, we allow the risk of flooding to increase over time. Over our 50-year time horizon, we double the risk of 100- and 500-year flood events to account for the effects of sea level rise on coastal flooding. Based on the economic analysis, the project is highly cost beneficial over its 50-year timeframe. This analysis demonstrates that climate change adaptation investments can be cost beneficial even though they mitigate the impacts of low-probability, high-consequence events.