Die oligomerisasie van Sasol alfa-olefienfraksies

M.Sc.The development of synthetic lubricants was the logical result of high demands being made by modern technology, the exhaustion of natural mineral oil sources and the search for environmentally friendly substances. Alpha olefins are products of the Sasol Fischer-Tropsch process and are currently part of the wider petrol pool. Substantial value can be added to the alpha olefins by the production of high value polyalphaolefins (PADs). This project was aimed at finding explanations for previous unsuccessful attempts to produce acceptable PADs from Sasol feedstreams. High priority was given to the modification of experimental procedures to produce a synthetic oil that conforms to specific standards. Oxygenates, aromatics and "other than alpha" olefins (branched, internal and cyclic olefins) were identified as problem components in the Sasol feedstream. These compounds led to early termination of oligomerisation and in the presence of BF3 , unwanted compounds were even incorporated into the PAD products. The feedstream was thus purified by distillation and a MeDH/H2D extraction procedure. As a result, better reaction control (with regard to oligomer distribution) was gained and the product quality improved. Reaction conditions were optimised and basic reaction models (to predict oligomer distributions) were developed. It became clear however, that product quality did not only depend on oligomer distribution, but also on the specific structures present in the various oligomers. GC analyses showed that each oligomer consists of a great number of isomers - even more than can be explained in terms of the classic cationic mechanism for oligomerisation. GC-MS analyses could not successfully distinguish between different branched isomers, because of the complexity of the mixture. Summary The question was asked whether the complex mixture has already been formed during the primary oligomerisation process, or at a later stage by skeletal rearrangements. Research work indicated that one can distinguish between a primary (normal oligomerisation) process, and a secondary process (skeletal rearrangement). It became clear that the secondary process is favoured by specific reaction conditions (e.g. long reaction times and high co-catalyst concentrations). The formation of isomers increased under these conditions and product quality was adversely affected. The possibility to produce PAD products from Sasol feedstreams identical to commercial products still exists, and necessitate further research work

Environmental controls, morphodynamic processes, and ecogeomorphic interactions of barchan to parabolic dune transformations

The transformation of barchans into parabolic dunes has been observed in various dune systems around the world. Precise details of how environmental controls influence the dune transformation and stabilisation mechanism, however, remain poorly understood. A ‘horns-anchoring’ mechanism and a ‘nebkhas-initiation’ mechanism have previously been proposed and selected environmental controls on the transformation have been explored by some modelling efforts, but the morphodynamic processes and eco-geomorphic interactions involved are unclear and comparison between different dune systems is challenging. This study extends a cellular automaton model, informed by empirical data from fieldwork and remote sensing, to fully explore how vegetation characteristics, boundary conditions, and wind regime influence the transformation process and the resulting dune morphologies. A ‘dynamic growth function’ is introduced for clump-like perennials to differentiate between growing and non-growing seasons and to simulate the development of young plants into mature plants over multiple years. Modelling results show that environmental parameters interact with each other in a complex manner to impact the transformation process. The study finds a fundamental power-law relation between a non-dimensional parameter group, so-called the ‘dune stabilising index’ (S⁎), and the normalised migration distance of the transforming dune, which can be used to reconstruct paleo-environmental conditions and monitor the impacts of changes in climate or land-use on a dune system. Four basic eco-geomorphic interaction zones are identified which bear different functionality in the barchan to parabolic dune transformation. The roles of different environmental controls in changing the eco-geomorphic interaction zones, transforming processes, and resulting dune morphologies are also clarified

The Relationship between the Soil Seed Bank and Above-Ground Vegetation of a Coastal Barrier Island

The germinable soil seed bank is described from a coastal barrier island off the northwest coast of Florida, USA. Soil samples collected from seven vegetation types, recently deposited dredge spoil and unvegetated areas in autumn 1990 and spring 1991 were placed out in greenhouse trays. 110 taxa germinated from the samples with the largest number (41) being C3 perennial dicots. The largest number of taxa germinated from dry (57) and wet (54) swales, the fewest (one species: Heterotheca subaxillaris) from strand. Similarity of seed bank densities to above-ground species cover was low (Jaccard’s Index = 0.36), not different between vegetation types, but higher in the autumn than in the following spring. Compositional gradients in the seed bank and above-ground vegetation determined using DCA ordination were highly correlated and related to distance from mean high water, and plot elevation. At the landscape scale, the seed bank provided an equally clear delineation of vegetation types to that based upon the above-ground vegetation. The seed bank of low disturbance, late-succession vegetation types (wooded dunes, swales, marshes) was well developed (high species richness, emergent density, and percentage annual species) with the exception that the large-seeded woody species (i.e. Quercus spp.) were absent from the wooded dune seed bank. By contrast, a poorly developed and transient seed bank occurred in more frequently disturbed (extensive sand movement, salt spray), early successional dredge spoil, unvegetated areas and strand. These contrasts support a general pattern of increasing seed bank development and a persistent rather than transient seed bank with decreasing disturbance frequency, increasing time since disturbance and successional maturity

Primary succession in an Atlantic saltmarsh: from intertidal flats to mid-marsh platform in 35 years

Although salt marsh is a classic example of primary succession, the underlying mechanisms and their time-scales are poorly understood. As salt marsh succession depends on sediment accretion, the amelioration of abiotic conditions associated with increasing elevation suggests potential explanatory roles for facilitation, competition and the stress-gradient hypothesis. We present a 35-year longitudinal study of salt marsh development from intertidal flat to a mid-marsh platform at Odiel Marshes in south-western Iberia. Using permanent plots, this work chronicles changes in elevation and marsh morphology, their evolving effects on sediment redox potential and salinity and the colonisation and changing patterns of dominance of halophytic species. Sporadically colonising clumps of the low-marsh species Spartina maritima trapped sediment to form raised tussocks, which increased in elevation and area. Reduced tidal inundation and locally improved drainage promoted higher redox potentials and allowed colonisation by a sequence of species less tolerant of reducing conditions: Sarcocornia perennis, its hybrid with high-marsh S. fruticosa, and Atriplex portulacoides. Unlike its centrifugally colonising predecessors, A. portulacoides invaded from the tussock edges. Transplant experiments designed to investigate its late establishment on tussocks showed that seedling survival depended on elevational differences as small as 4 cm. After increasing in elevation by c. 1 m (c. 29 mm/year), coalescence of the tussocks formed a marsh platform at a level corresponding to mean high tides. This supports a theoretical punctuated transition from ‘submergence marsh’ to ‘emergence marsh’, previously postulated for this tidal elevation. Synthesis. The unexpected rapidity of this primary succession highlights the central role of facilitation. Vertical sediment accretion, locally engineered by colonising species, progressively alleviates abiotic stress and allows colonisation by species that are less tolerant of chemically reducing conditions but are ultimately better competitors

Functional Interactions between KCNE1 C-Terminus and the KCNQ1 Channel

The KCNE1 gene product (minK protein) associates with the cardiac KvLQT1 potassium channel (encoded by KCNQ1) to create the cardiac slowly activating delayed rectifier, IKs. Mutations throughout both genes are linked to the hereditary cardiac arrhythmias in the Long QT Syndrome (LQTS). KCNE1 exerts its specific regulation of KCNQ1 activation via interactions between membrane-spanning segments of the two proteins. Less detailed attention has been focused on the role of the KCNE1 C-terminus in regulating channel behavior. We analyzed the effects of an LQT5 point mutation (D76N) and the truncation of the entire C-terminus (Δ70) on channel regulation, assembly and interaction. Both mutations significantly shifted voltage dependence of activation in the depolarizing direction and decreased IKs current density. They also accelerated rates of channel deactivation but notably, did not affect activation kinetics. Truncation of the C-terminus reduced the apparent affinity of KCNE1 for KCNQ1, resulting in impaired channel formation and presentation of KCNQ1/KCNE1 complexes to the surface. Complete saturation of KCNQ1 channels with KCNE1-Δ70 could be achieved by relative over-expression of the KCNE subunit. Rate-dependent facilitation of K+ conductance, a key property of IKs that enables action potential shortening at higher heart rates, was defective for both KCNE1 C-terminal mutations, and may contribute to the clinical phenotype of arrhythmias triggered by heart rate elevations during exercise in LQTS mutations. These results support several roles for KCNE1 C-terminus interaction with KCNQ1: regulation of channel assembly, open-state destabilization, and kinetics of channel deactivation

Herbivore regulation of plant abundance in aquatic ecosystems.

Herbivory is a fundamental process that controls primary producer abundance and regulates energy and nutrient flows to higher trophic levels. Despite the recent proliferation of small-scale studies on herbivore effects on aquatic plants, there remains limited understanding of the factors that control consumer regulation of vascular plants in aquatic ecosystems. Our current knowledge of the regulation of primary producers has hindered efforts to understand the structure and functioning of aquatic ecosystems, and to manage such ecosystems effectively. We conducted a global meta-analysis of the outcomes of plant-herbivore interactions using a data set comprised of 326 values from 163 studies, in order to test two mechanistic hypotheses: first, that greater negative changes in plant abundance would be associated with higher herbivore biomass densities; second, that the magnitude of changes in plant abundance would vary with herbivore taxonomic identity. We found evidence that plant abundance declined with increased herbivore density, with plants eliminated at high densities. Significant between-taxa differences in impact were detected, with insects associated with smaller reductions in plant abundance than all other taxa. Similarly, birds caused smaller reductions in plant abundance than echinoderms, fish, or molluscs. Furthermore, larger reductions in plant abundance were detected for fish relative to crustaceans. We found a positive relationship between herbivore species richness and change in plant abundance, with the strongest reductions in plant abundance reported for low herbivore species richness, suggesting that greater herbivore diversity may protect against large reductions in plant abundance. Finally, we found that herbivore-plant nativeness was a key factor affecting the magnitude of herbivore impacts on plant abundance across a wide range of species assemblages. Assemblages comprised of invasive herbivores and native plant assemblages were associated with greater reductions in plant abundance compared with invasive herbivores and invasive plants, native herbivores and invasive plants, native herbivores and mixed-nativeness plants, and native herbivores and native plants. By contrast, assemblages comprised of native herbivores and invasive plants were associated with lower reductions in plant abundance compared with both mixed-nativeness herbivores and native plants, and native herbivores and native plants. However, the effects of herbivore-plant nativeness on changes in plant abundance were reduced at high herbivore densities. Our mean reductions in aquatic plant abundance are greater than those reported in the literature for terrestrial plants, but lower than aquatic algae. Our findings highlight the need for a substantial shift in how biologists incorporate plant-herbivore interactions into theories of aquatic ecosystem structure and functioning. Currently, the failure to incorporate top-down effects continues to hinder our capacity to understand and manage the ecological dynamics of habitats that contain aquatic plants

Movements of marine fish and decapod crustaceans: Process, theory and application

Many marine species have a multi-phase ontogeny, with each phase usually associated with a spatially and temporally discrete set of movements. For many fish and decapod crustaceans that live inshore, a tri-phasic life cycle is widespread, involving: (1) the movement of planktonic eggs and larvae to nursery areas; (2) a range of routine shelter and foraging movements that maintain a home range; and (3) spawning migrations away from the home range to close the life cycle. Additional complexity is found in migrations that are not for the purpose of spawning and movements that result in a relocation of the home range of an individual that cannot be defined as an ontogenetic shift. Tracking and tagging studies confirm that life cycle movements occur across a wide range of spatial and temporal scales. This dynamic multi-scale complexity presents a significant problem in selecting appropriate scales for studying highly mobile marine animals. We address this problem by first comprehensively reviewing the movement patterns of fish and decapod crustaceans that use inshore areas and present a synthesis of life cycle strategies, together with five categories of movement. We then examine the scale-related limitations of traditional approaches to studies of animal-environment relationships. We demonstrate that studies of marine animals have rarely been undertaken at scales appropriate to the way animals use their environment and argue that future studies must incorporate animal movement into the design of sampling strategies. A major limitation of many studies is that they have focused on: (1) a single scale for animals that respond to their environment at multiple scales or (2) a single habitat type for animals that use multiple habitat types. We develop a hierarchical conceptual framework that deals with the problem of scale and environmental heterogeneity and we offer a new definition of 'habitat' from an organism-based perspective. To demonstrate that the conceptual framework can be applied, we explore the range of tools that are currently available for both measuring animal movement patterns and for mapping and quantifying marine environments at multiple scales. The application of a hierarchical approach, together with the coordinated integration of spatial technologies offers an unprecedented opportunity for researchers to tackle a range of animal-environment questions for highly mobile marine animals. Without scale-explicit information on animal movements many marine conservation and resource management strategies are less likely to achieve their primary objectives

How does vegetation affect sedimentation on tidal marshes? Investigating particle capture and hydrodynamic controls on biologically mediated sedimentation

Plants are known to enhance sedimentation on intertidal marshes. It is unclear, however, if the dominant mechanism of enhanced sedimentation is direct organic sedimentation, particle capture by plant stems, or enhanced settling due to a reduction in turbulent kinetic energy within flows through the plant canopy. Here we combine several previously reported laboratory studies with an 18 year record of salt marsh macrophyte characteristics to quantify these mechanisms. In dense stands of Spartina alterniflora (with projected plant areas per unit volume of >10 m 121) and rapid flows (>0.4 m s 121), we find that the fraction of sedimentation from particle capture can instantaneously exceed 70%. In most marshes dominated by Spartina alterniflora, however, we find particle settling, rather than capture, will account for the majority of inorganic sedimentation. We examine a previously reported 2 mm yr 121 increase in accretion rate following a fertilization experiment in South Carolina. Prior studies at the site have ruled out organic sedimentation as the cause of this increased accretion. We apply our newly developed models of particle capture and effective settling velocity to the fertilized and control sites and find that virtually all (>99%) of the increase in accretion rates can be attributed to enhanced settling brought about by reduced turbulent kinetic energy in the fertilized canopy. Our newly developed models of biologically mediated sedimentation are broadly applicable and can be applied to marshes where data relating biomass to stem diameter and projected plant area are available

The application of δ13C, TOC and C/N geochemistry to reconstruct Holocene relative sea levels and paleoenvironments in the Thames Estuary, UK

We examined the use of δ13C, TOC and C/N geochemistry of sedimentary organic matter to reconstruct former sea levels and paleoenvironments in the absence of suitable microfossil data. The modern distribution of δ13C, TOC and C/N of 33 vegetation and 74 surface sediment samples collected from four coastal wetlands in the Thames Estuary and Norfolk, UK are described. The δ13C, TOC and C/N geochemistry of sediments varied in relation to the input of in situ vascular vegetation versus allochthonous particulate organic matter and algae, which was controlled primarily by tidal inundation. We reviewed published and unpublished studies to produce an English database of vegetation (n = 257) and sediment (n = 132) δ13C, TOC and C/N geochemistry. Four elevation-dependent environments in the database had statistically distinct δ13C, TOC and C/N values: (1) tidal flat/low marsh (δ13C: −24.9 ± 1.2‰; TOC: 3.6 ± 1.7%; C/N: 9.9 ± 0.8); (2) middle marsh/high (δ13C: −26.2 ± 1.0‰; TOC: 9.8 ± 6.7%; C/N: 12.1 ± 1.8); (3) reed swamp (δ13C: −27.9 ± 0.7‰: TOC: 36.5 ± 11.5%; C/N: 13.9 ± 1.2); and (4) fen carr (δ13C: −29.0 ± 0.6‰; TOC: 41.6 ± 5.7%; C/N: 17.4 ± 3.1). The δ13C, TOC and C/N geochemistry database was applied to a Holocene sediment core collected from the Thames Estuary to produce three new sea-level index points and one limiting date, illustrating the utility of δ13C, TOC and C/N values to reconstruct Holocene relative sea levels