Degradation of metals through atmospheric corrosion is a most important and costly phenomenon with significant effects on, e.g., the lifespan of industrial materials, the reliability of electronic components and military equipment, and the aesthetic appearance of our cultural heritage. Atmospheric corrosion is the result of the interaction between the metal and its atmospheric environment, and occurs in the presence of a thin aqueous adlayer. The common incorporation of pollutant species into this adlayer usually enhances the degradation process. During atmospheric corrosion indoors, low concentrations of organic atmospheric constituents, such as formic, acetic, propionic, butyric and oxalic acids, have found to play an accelerating role on a broad range of metals or their alloys, including lead, steel, nickel, copper, cadmium, magnesium and zinc. In this doctoral thesis the initial stages of the atmospheric corrosion of copper exposed to synthetic air, aiming at simulating representative indoor atmospheric environments, have been investigated both experimentally and through a computational method. The experiments have been based on a unique analytical setup in which a quartz crystal microbalance (QCM) was integrated with infrared reflection absorption spectroscopy (IRAS). This enabled the initial atmospheric corrosion of copper to be analyzed during ongoing corrosion in humidified air at room temperature and additions of 120 ppb (parts per volume billions) of acetic, formic or propionic acid. The main phases identified were copper (I) oxide (Cu2O) and various forms of copper carboxylate, and their amounts deduced with the different analytical techniques agree with a relative accuracy of 12% or better. Particular emphasis has been on the identification of different forms of copper (I) oxide generated during these exposures. An electrochemically based model has been proposed to describe how copper oxides, formed in the presence of acetic acid, are electrochemically reduced in neutral solution. The model includes the electrochemical reduction of copper (II) oxide (CuO), amorphous copper (I) oxide (Cu2O)am, intermediate copper (I) oxide (Cu2O)in, and crystalline copper (I) oxide (Cu2O)cr. A good agreement is obtained between the model and experimental data, which supports the idea of a reduction sequence which starts with copper (II) oxide and continues with the reduction of the three copper (I) oxides at more negative potentials. The quantified analytical data obtained in this doctoral study on corrosion products formed on copper, and corresponding data on zinc reported elsewhere, were used as the starting point to develop a computational model, GILDES, that describes the atmospheric corrosion processes involved. GILDES considers the whole interfacial regime in which all known chemical reactions have been considered which are assumed to govern the initial atmospheric corrosion of copper or zinc in the presence of carboxylic acids. The model includes two separate pathways, a proton-induced dissolution of cuprous ions or zinc ions followed by the formation of either copper (I) oxide or zinc (II) oxide, and a carboxylate-induced dissolution followed by the formation of either copper (II) carboxylate or zinc (II) carboxylate. The model succeeds to predict the two main phases in the corrosion products and a correct ranking of aggressiveness of the three acids for both copper and zinc. The ranking has been attributed to differences in acid dissociation constant and deposition velocity of the carboxylic acids investigated. / QC 20111114

A riparian ecosystem is the area between the aquatic and terrestrial setting of a stream, and serves as a corridor and habitat for birds. Several riparian ecosystems are located in urban environments, and three main riparian corridors are located in Potchefstroom. They are the Mooi River, Wasgoed Spruit, and Spitskop Spruit, which encompass a wide range of different vegetation types and anthropogenic factors. Therefore, different habitat types for birds occur along the riparian corridors of Potchefstroom. Factors such as food and water availability, nesting sites, competition, predation, learning, presence of other species, and those species that are able to adapt to environmental changes influence the avian diversity and communities along riparian corridors. The hypothesis is that bird variables along the riparian corridors in Potchefstroom are affected by vegetation, anthropogenic, and seasonal influences. To investigate these affects, two secondary objectives were formulated. The first was to characterise riparian avian habitats (CAHs) according to vegetation and anthropogenic factors, and the second was to identify temporal and spatial changes in avian variables. The three streams were divided into 79 consecutive transects, each 300 m long. The study area consisted of: 17 transects along Spitskop Spruit, 12 along Wasgoed Spruit and 50 along the Mooi River. Bird observations were conducted monthly from June 2006 to June 2007. Birds that were observed with a perpendicular distance ≤ 30 meters towards the streams were included in the results. The bird species that were observed were also classified into different nesting and feeding guilds. Environmental data recorded included: vegetation structure (estimated cover percentages and height classes of trees, shrubs, grasses, herbs, sedges, and reeds), anthropogenic structures (estimated cover percentages of roads, footpaths, bridges, electrical pylons, houses, and drainage pipes), and the presence of informal settlers along each transect (the mean number of people and the space they occupy). Vegetation was monitored in summer– (February 2007 until April 2007) and winter months (June 2007 until August 2007). The anthropogenic structures and the presence of informal settlers (anthropogenic factors) were monitored simultaneously with the bird counts. Transect-time profiles were drawn for the four parameters, which differed on spatial and time scales. Multivariate analyses included non-metric multidimensional scaling (NMS), cluster analysis, and indicator species analysis. Cluster analyses and NMS bi-plots were used to define characterised avian habitats (CAHs). Two types of CAHs were characterised: Summer CAHs (summer vegetation and anthropogenic factors) and Anthropogenically CAHs (Anthropogenic factors alone). Bird species were then ordinated with the summer and anthropogenically CAHs on NMS successional vector graphs. The successional vectors illustrate the avian community trajectories of the different CAHs. Indicator species analyses were performed to describe associations between the bird species and the summer and anthropogenically CAHs. The summer and anthropogenic CAHs that were characterised had different avian community trajectories and different species were associated with these CAHs. Different levels in avian diversity appeared among these CAHs, and convergence and divergence in communities appeared among these CAHs. Birds also selected their habitats according to feeding and nesting behaviours. Consequently, it can be deduced that environmental factors such as vegetation structures and anthropogenic factors, as well as seasonality, had an effect on the distribution of birds along the riparian corridors of Potchefstroom. / Thesis (Master of Environmental Sciences)--North-West University, Potchefstroom Campus, 2013

A riparian ecosystem is the area between the aquatic and terrestrial setting of a stream, and serves as a corridor and habitat for birds. Several riparian ecosystems are located in urban environments, and three main riparian corridors are located in Potchefstroom. They are the Mooi River, Wasgoed Spruit, and Spitskop Spruit, which encompass a wide range of different vegetation types and anthropogenic factors. Therefore, different habitat types for birds occur along the riparian corridors of Potchefstroom. Factors such as food and water availability, nesting sites, competition, predation, learning, presence of other species, and those species that are able to adapt to environmental changes influence the avian diversity and communities along riparian corridors. The hypothesis is that bird variables along the riparian corridors in Potchefstroom are affected by vegetation, anthropogenic, and seasonal influences. To investigate these affects, two secondary objectives were formulated. The first was to characterise riparian avian habitats (CAHs) according to vegetation and anthropogenic factors, and the second was to identify temporal and spatial changes in avian variables. The three streams were divided into 79 consecutive transects, each 300 m long. The study area consisted of: 17 transects along Spitskop Spruit, 12 along Wasgoed Spruit and 50 along the Mooi River. Bird observations were conducted monthly from June 2006 to June 2007. Birds that were observed with a perpendicular distance ≤ 30 meters towards the streams were included in the results. The bird species that were observed were also classified into different nesting and feeding guilds. Environmental data recorded included: vegetation structure (estimated cover percentages and height classes of trees, shrubs, grasses, herbs, sedges, and reeds), anthropogenic structures (estimated cover percentages of roads, footpaths, bridges, electrical pylons, houses, and drainage pipes), and the presence of informal settlers along each transect (the mean number of people and the space they occupy). Vegetation was monitored in summer– (February 2007 until April 2007) and winter months (June 2007 until August 2007). The anthropogenic structures and the presence of informal settlers (anthropogenic factors) were monitored simultaneously with the bird counts. Transect-time profiles were drawn for the four parameters, which differed on spatial and time scales. Multivariate analyses included non-metric multidimensional scaling (NMS), cluster analysis, and indicator species analysis. Cluster analyses and NMS bi-plots were used to define characterised avian habitats (CAHs). Two types of CAHs were characterised: Summer CAHs (summer vegetation and anthropogenic factors) and Anthropogenically CAHs (Anthropogenic factors alone). Bird species were then ordinated with the summer and anthropogenically CAHs on NMS successional vector graphs. The successional vectors illustrate the avian community trajectories of the different CAHs. Indicator species analyses were performed to describe associations between the bird species and the summer and anthropogenically CAHs. The summer and anthropogenic CAHs that were characterised had different avian community trajectories and different species were associated with these CAHs. Different levels in avian diversity appeared among these CAHs, and convergence and divergence in communities appeared among these CAHs. Birds also selected their habitats according to feeding and nesting behaviours. Consequently, it can be deduced that environmental factors such as vegetation structures and anthropogenic factors, as well as seasonality, had an effect on the distribution of birds along the riparian corridors of Potchefstroom. / Thesis (Master of Environmental Sciences)--North-West University, Potchefstroom Campus, 2013