Inter-annual stability of land cover classification: explorations and improvements

Land cover information is a key input to many earth system models, and thus accurate and consistent land cover maps are critically important to global change science. However, existing global land cover products show unrealistically high levels of year-to-year change. This thesis explores methods to improve accuracies for global land cover classifications, with a focus on reducing spurious year-to-year variation in results derived from MODIS data. In the first part of this thesis I use clustering to identify spectrally distinct sub-groupings within defined land cover classes, and assess the spectral separability of the resulting sub-classes. Many of the sub-classes are difficult to separate due to a high degree of overlap in spectral space. In the second part of this thesis, I examine two methods to reduce year-to-year variation in classification labels. First, I evaluate a technique to construct training data for a per-pixel supervised classification algorithm by combining multiple years of spectral measurements. The resulting classifier achieves higher accuracy and lower levels of year-to-year change than a reference classifier trained using a single year of data. Second, I use a spatio-temporal Markov Random Field (MRF) model to post-process the predictions of a per-pixel classifier. The MRF framework reduces spurious label change to a level comparable to that achieved by a post-hoc heuristic stabilization technique. The timing of label change in the MRF processed maps better matched disturbance events in a reference data, whereas the heuristic stabilization results in label changes that lag several years behind disturbance events

Structural and spectroscopic characterisation of C4 oxygenates relevant to structure/activity relationships of the hydrogenation of α,β-unsaturated carbonyls

In the present work, we have investigated the conformational isomerism and calculated the vibrational spectra of the C4 oxygenates: 3-butyne-2-one, 3-butene-2-one, 2-butanone and 2-butanol using density functional theory. The calculations are validated by comparison to structural data where available and new, experimental inelastic neutron scattering and infrared spectra of the compounds. We find that for 3-butene-2-one and 2-butanol the spectra show clear evidence for the presence of conformational isomerism and this is supported by the calculations. Complete vibrational assignments for all four molecules are provided and this provides the essential information needed to generate structure/activity relationships for the sequential catalytic hydrogenation of 3-butyne-2-one to 2-butanol

Computer Security Policy: Preventing Vulnerabilities and the Impact of Selective Enforcement On an Organization

This project focuses on the importance of a computer security policy as a whole. It also looks at how security policies assist in preventing vulnerabilities that may be instigated by employees. Moreover, the project views how the concept of selective enforcement can affect and impact an organization. This project delves into actual cases of employee misconduct in various organizations. It explains how policies were violated and the repercussions of these various misdeeds. Finally the project discusses different items that a good security policy should have and how important it is for policies to be enforced. It is vital that an organization inform its employees of what is appropriate and who is responsible for the use of technology in the workplace. This project finds that the protection of a company\u27s and an employee\u27s privacy is important and what most individuals are concerned with. The exploitation of an employee\u27s trust and ignorance is what a policy can prevent

Miller–Urey spark-discharge experiments in the deuterium world

We designed and conducted a series of primordial-soup Miller-Urey style experiments with deuterated gases and reagents to compare the spark-discharge products of a “deuterated world” with the standard reaction in the “hydrogenated world”. While the deuteration of the system has little effect on the distribution of amino acid products, significant differences are seen in other regions of the product-space. Not only do we observe about 120 new species, we also see significant differences in their distribution if the two hydrogen isotope worlds are compared. Several isotopologue matches can be identified in both, but a large proportion of products have no equivalent in the corresponding isotope world with ca. 43 new species in the D world and ca. 39 new species in the H world. This shows that isotopic exchange (the addition of only one neutron) may lead to significant additional complexity in chemical space under otherwise identical reaction conditions

Structure/activity relationships applied to the hydrogenation of α,β-unsaturated carbonyls: The hydrogenation of 3-butyne-2-one over alumina-supported palladium catalysts

The gas phase hydrogenation of 3-butyne-2-one, an alkynic ketone, over two alumina-supported palladium catalysts is investigated using infrared spectroscopy in a batch reactor at 373 K. The mean particle size of the palladium crystallites of the two catalysts are comparable (2.4 ± 0.1 nm). One catalyst (Pd(NO3)2/Al2O3) is prepared from a palladium(II) nitrate precursor, whereas the other catalyst (PdCl2/Al2O3) is prepared using palladium(II) chloride as the Pd precursor compound. A three-stage sequential process is observed with the Pd(NO3)2/Al2O3 catalyst facilitating complete reduction all the way through to 2-butanol. However, hydrogenation stops at 2-butanone with the PdCl2/Al2O3 catalyst. The inability of the PdCl2/Al2O3 catalyst to reduce 2-butanone is attributed to the inaccessibility of edge sites on this catalyst, which are blocked by chlorine retention originating from the catalyst’s preparative process. The reaction profiles observed for the hydrogenation of this alkynic ketone are consistent with the site-selective chemistry recently reported for the hydrogenation of crotonaldehyde, an alkenic aldehyde, over the same two catalysts. Thus, it is suggested that a previously postulated structure/activity relationship may be generic for the hydrogenation of α,β-unsaturated carbonyl compounds over supported Pd catalysts

Inelastic neutron scattering studies of methyl chloride synthesis over alumina

Not only is alumina the most widely used catalyst support material in the world, it is also an important catalyst in its own right. One major chemical process that uses alumina in this respect is the industrial production of methyl chloride. This is a large scale process (650 000 metric tons in 2010 in the United States), and a key feedstock in the production of silicones that are widely used as household sealants. In this Account, we show how, in partnership with conventional spectroscopic and reaction testing methods, inelastic neutron scattering (INS) spectroscopy can provide additional insight into the active sites present on the catalyst, as well as the intermediates present on the catalyst surface.<p></p> INS spectroscopy is a form of vibrational spectroscopy, where the spectral features are dominated by modes involving hydrogen. Because of this, most materials including alumina are largely transparent to neutrons. Advantageously, in this technique, the entire “mid-infrared”, 0–4000 cm<sup>–1</sup>, range is accessible; there is no cut-off at 1400 cm<sup>–1</sup> as in infrared spectroscopy. It is also straightforward to distinguish fundamental modes from overtones and combinations. <p></p> A key parameter in the catalyst’s activity is the surface acidity. In infrared spectroscopy of adsorbed pyridine, the shifts in the ring stretching modes are dependent on the strength of the acid site. However, there is a very limited spectral range available. We discuss how we can observe the low energy ring deformation modes of adsorbed pyridine by INS spectroscopy. These modes can undergo shifts that are as large as those seen with infrared inspectroscopy, potentially enabling finer discrimination between acid sites. <p></p> Surface hydroxyls play a key role in alumina catalysis, but in infrared spectroscopy, the presence of electrical anharmonicity complicates the interpretation of the O–H stretch region. In addition, the deformations lie below the infrared cut-off. Both of these limitations are irrelevant to INS spectroscopy, and all the modes are readily observable. When we add HCl to the catalyst surface, the acid causes changes in the spectra. We can then deduce both that the surface chlorination leads to enhanced Lewis acidity and that the hydroxyl group must be threefold coordinated. <p></p> When we react η-alumina with methanol, the catalyst forms a chemisorbed methoxy species. Infrared spectroscopy clearly shows its presence but also indicates the possible coexistence of a second species. Because of INS spectroscopy’s ability to discriminate between fundamental modes and combinations, we were able to unambiguously show that there is a single intermediate present on the surface of the active catalyst. This work represents a clear example where an understanding of the chemistry at the molecular level can help rationalize improvements in a large scale industrial process with both financial and environmental benefits. <p></p&gt