Deconstructing Adsorption Variability: Investigating Controls on Pesticide Adsorption in Soil and Modelling Koc

Due to potential environmental risks of pesticides, it is important that the fate of pesticides is known and that safer pesticides are developed in the future. This thesis focused on identifying controls on the Koc of pesticides in soil based on their structural parameters. This thesis also developed quantitative structure-activity relationship (QSAR) models to predict the environmental fate of new pesticides. To understand the controls on Koc, a range of multivariate statistical techniques were used including; principal component analysis, and analysis of variance. Predictive models were created using logistic regression, and multiple linear regression. The study found adsorption of pesticides in soil is controlled by a combination of size and solubility parameters. Logistic regression models were able to predict the adsorption potential of metabolites, relative to their parent based on metabolite structures. This study found that adsorption behaviour of pesticides was fairly specific to different chemical groups. A QSAR model for Koc was constructed for a group of early stage compounds and could predict Koc to just over an order of magnitude. The results of this study have implications for the pesticide development process. If developed further to include a wider range of chemical groups then the models have the potential to reduce the dependence on laboratory tests in the early stages of the development process. However, this study also questions the use of Koc as a predictive parameter and offers alternative solutions to predicting environmental fate of pesticides

Cretaceous and Cenozoic Basin Evolution Based on Decompacted Sediment Thickness from Petroleum Wells around New Zealand

Decompacted sedimentary data from 33 New Zealand exploration wells is used to investigate basin evolution and tectonics from around New Zealand. This analysis is directed to both a comparison of basin behaviour and a search for common subsidence signatures. Common to almost all New Zealand basin subsidence curves is a sedimentary signature associated with rifting of the Gondwana super-continent (80-65 Ma). In the Great South Basin a second rifting event is inferred at 51 [plus or minus] 2 Ma, illustrated by a rapid increase in subsidence rates (with a maximum rate of 190 m.Myr-1 at Pakaha-1). Coinciding with the cessation of Tasman Sea rifting ([approximately] 53 Ma), and with the onset of rifting in the Emerald Basin ([approximately] 50 Ma), it is assumed that the event is related to the tectonic plate reorganization. An increase in sedimentation is noted at [approximately] 20 Ma in most South Island wells. Convergence on the Alpine Fault, leading to increased erosion is cited as a mechanism for this period of basin growth, consistent with the Cande and Stock (2004) model of plate motions. A second increase in sedimentation occurs at [approximately] 6 Ma in almost all wells around New Zealand. Climate-driven erosion resulting in isostatic uplift is thought to contribute to this event. Hiatuses in the sedimentary record for the Canterbury, Great South and Western Southland Basins during the late Oligocene are interpreted as the Marshall Paraconformity. It appears that the break in sedimentation located within a regional transgressional mega-sequence was caused by mid Oligocene glacio-eustatic fall and related oceanic current processes. Loading by the Northland Allochthon, in conjunction with paleobathymetry and subsidence data, is used to demonstrate the mechanical properties of the lithosphere. A lithospheric rigidity of 1.5 x [10 to the power of 22] Nm is estimated, with an elastic thickness of 12 km. Considerably lower than elastic thickness values previously calculated for the Plio-Pleistocene loading of the Taranaki Platform. It is noted that the Northland value represents a younger, hotter crust at the time of load emplacment. With the exception of the central Taranaki and Great South Basins, stretching factors ([Beta]) for the sedimentary basins surrounding New Zealand are below 2. This suggests crustal thickness prior to rifting was between 35 and 50 km, consistent with data from conjugate margins of Australia and Antarctica. An increase in water depth in the Taranaki Basin at 25 [plus or minus] 3 Ma is confirmed by this study. This coincides with a similar signature on the West Coast of the South Island at 26 [plus or minus] 2 Ma. It is suggested that a mantle flow caused by the initiation of the subduction zone at [approximately] 25 Ma extends over a broader region (>750 km) than previously thought

"Pengaruh Ukuran Perusahaan, Leverage Dan Profitabilitas Terhadap Pelaporan Keuangan Melalui Internet/(Internet Financial Reporting) (Studi Pada Perusahaan Sektor Industri Barang Konsumsi Yang Terdaftar Di Bursa Efek Indonesia Tahun 2019) "

"Christie Roselinda Louise Sara, 2021. “Pengaruh Ukuran Perusahaan, Leverage dan Profitabilitas Terhadap Pelaporan Keuangan Melalui Internet (Internet Financial Reporting) (Studi Pada Perusahaan Sektor Industri Barang Konsumsi yang Terdaftar di Bursa Efek Indonesia Tahun 2019)“ Mengungkapkan infromasi melalui internet atau Internet Financial Reporting (IFR) merupakan hal yang dilakukan perusahaan seiring dengan perkembangan teknologi. Pelaporan dilakukan dengan mengunggah informasi melalui website perusahaan. Dengan melakukan hal tersebut diharapkan pengguna internet atau pihak internal dan eksternal yang berkaitan dengan perusahaan akan dengan mudah mengakses informasi yang ingin didapatkan dari perusahaan yang dituju, juga mengunduh, dan menganalisa data. Tujuan dari penelitian ini ialah untuk mengatahui pengaruh variabel Ukuran Perusahaan, Leverage, dan Profitabilitas terhadap Internet Financial Reporting pada perusahaan sektor industri barang konsumsi yang terdaftar di BEI periode 2019. Penelitian dilakukan dengan jenis explanatory research. Objek yang diteliti ialah perusahaan sektor industri barang konsumsi periode 2019 dengan jumlah 45 perusahaan. Teknik analisis data yang digunakan dalam penelitian ini ialah statistik deskriptif, uji asumsi klasik, dan pengujian hipotesis. Hasil dari penelitian ini menunjukkan bahwa variabel ukuran perusahaan berpengaruh positif dan signifikan terhadap pelaporan keuangan melalui internet, tetapi variabel leverage dan profitabilitas berpengaruh negatif signifikan terhadap pelaporan keuangan melalui internet/ Internet Financial Reporting (IFR). Kata Kunci : Internet Financial Reporting, Ukuran Perusahaan, Leverage, Profitabilitas.

TESS – Tidlig Engelsk Sprog Start på Brøndby Strand Skole

TESS, som står for Tidlig Engelsk Sprog Start, blev indført på Søholtskolen i Brøndby i 2004, hvor én af [...

A critical analysis of the income tax implications of conditional employee share plans in South Africa

Employee share plans are commonly used to provide a staff incentive to employees who have served long and continuously, as well as to compensate the employees for their commitment in reaching company goals and performance criteria. Because any person, including employers implementing such schemes, will always structure transactions to achieve the best possible tax outcome, many schemes and structures have become available to achieve those ends. A recent employee share scheme was structured through the incorporation of a wholly- owned subsidiary, which was incorporated for the sole purpose of administering and managing the employee share plan on behalf of the holding company. This would include acquiring holding company shares in the open market and the subsequent transfer thereof to the holding company’s employees. The payment made to the subsidiary for the services rendered and to enable the subsidiary to acquire holding company shares in the open market, was structured as a fee together with a risk premium payable and not as an intercompany interest-free loan. A study of the investigation and evaluation of the adequacy and legality of such schemes and structures and whether or not appropriate tax principles were applied to achieve possible tax benefits, creates several research challenges. Although previous research has been conducted on the tax implications for employees under a share-based plan, payments structured as interest-free loans and several case law on the deductibility of payments structured as interest-free loans, there is a lack of extensive previous academic research on the funding of employee share plans structured as a fee together with a risk premium, made to wholly-owned subsidiaries to manage and administer an employee share plan. The aim of this study is to help to fill the gap in relevant research, case law and legislation regarding the tax implications of this new funding structure of conditional employee share plans. The tax implications for both the holding company and the subsidiary will be taken into consideration to assess whether or not the scheme will be beneficial to all parties involved. AFRIKAANS : Aandeelgebaseerde skemas vir werknemers word algemeen gebruik om personeelvoordele aan werknemers te verskaf wat lang en deurlopende diens gelewer het, asook om vergoeding te bied aan werknemers vir hul toewyding in die bereiking van die maatskappy se doelwitte en prestasie-kriteria. Verskeie skemas en strukture het al ontstaan as gevolg van die feit dat enige persoon, onder wie werkgewers wat sulke skemas implementeer, deurgans transaksies sal struktureer om die beste moontlike belastinguitkoms te bewerkstellig. ’n Onlangse aandeelgebaseerde skema vir werknemers is soos volg gestruktureer: Die houermaatskappy het ’n volfiliaal ingelyf met die uitsluitlike doel om die administrasie en bestuur van die aandeelgebaseerde skema, namens die houermaatskappy te onderneem. Die verkryging van die houermaatskappy-aandele in die ope mark en die daaropvolgende oordrag daarvan aan die houermaatskappy se werknemers is beplan. Die betaling aan die filiaal vir die dienste gelewer en om die filiaal in staat te stel om die houermaatskappy se aandele in die ope mark te bekom, is gestruktureer as ’n fooi en ’n risiko-premie betaalbaar eerder as ’n rentevrye intergroep-lening as sodanig. ’n Studie oor die ondersoek en evaluering van die geskiktheid en wettigheid van sulke strukture en of die korrekte belastingbeginsels toegepas is om moontlike belastingvoordele te bereik, skep verskeie navorsingsuitdagings. Hoewel vorige navorsing onderneem is oor die belastingimplikasies vir werknemers in die lig van aandeelgebaseerde transaksies, betalings wat gestruktureer is as rentevrye lenings en verskeie wetsbepalings ten opsigte van die aftrekbaarheid van betalings wat gestruktureer is as rentevrye lenings, is daar ’n gebrek aan uitgebreide vorige akademiese navorsing oor die befondsing van aandeelgebaseerde skemas deur ’n fooi insluitende ’n risikopremie. Die doel van hierdie studie is om te help om die die gaping in relevante navorsing, regspraak en wetgewing ten opsigte van die belastingimplikasies van die nuwe finansieringstruktuur van voorwaardelike aandeelgebaseerde skemas vir werknemers te vernou. Die belastingimplikasies vir die houermaatskappy en filiaal sal in ag geneem word om vas te stel of die skema voordelig is vir albei die betrokke partye Copyright 2011, University of Pretoria. All rights reserved. The copyright in this work vests in the University of Pretoria. No part of this work may be reproduced or transmitted in any form or by any means, without the prior written permission of the University of Pretoria. Please cite as follows: Van Wyk, C-L 2011, A critical analysis of the income tax implications of conditional employee share plans in South Africa, MCom dissertation, University of Pretoria, Pretoria, viewed yymmdd F12/4/173/gmDissertation (MCom)--University of Pretoria, 2012.Taxationunrestricte

Synthesis of biodegradable microparticles for controlled active ingredient release

This thesis investigates the degradation and release of a fluorescent dye from biodegradable microparticles. Particular attention is given to determining the effect of polymeric properties on the subsequent microparticle degradation and release rate. Chapter 1 reviews the current polymerisation techniques for the synthesis of polyesters and introduces the synthetic procedures and degradability currently attainable for biodegradable microparticles. The concept of ‘smart’ release technology is introduced and the potential for using biodegradable ‘smart’ particles for enhanced agricultural formulations is explored. In Chapter 2, the ring-opening polymerisation (ROP) of a variety of polyesters is demonstrated, including an investigative study on the ROP of poly(3-hydroxybutyrate) (PHB) using magnesium 2,6-di-tert-butyl-4-methylphenoxide (Mg(BHT)2(THF)2). The polyesters are used to prepare microparticles via a single oil-in-water solvent evaporation technique, a range of formulation parameters are studied to enable optimisation of the subsequent particle size and stability. Chapter 3 investigates the encapsulation of a model fluorescent dye into poly(L-lactide) (PLLA) microparticles and the subsequent PLLA particle degradation and dye release under simulated environmental conditions is reported. Chapter 4 describes the degradation and release of 3-bromo-4-(butylamino)-2,5-dihydro-1H- pyrrole-2,5-dione (ABM) from a range of polyester microparticles, investigating the effect of polymer properties (e.g., molecular weight, crystallinity, etc.) on the particle degradation and release rate. In Chapter 5, the incorporation of a stimulus responsive polymer using optimised particle synthesis and degradation conditions (detailed in Chapter 2 and 3) is investigated. The successful tuneable microparticle degradation and release is described by incorporation of a light-responsive poly(nitrobenzyl malic acid) (PNO2BnMA) into homopolymer blends of PLLA microparticles. Chapter 6 explores the synthesis of degradable poly(vinyl acetate) (PVAc) microparticles by the incorporation of 2-methylene-1,3-dioxepane (MDO) degradable ester linkages into the polymer backbone via free radical ring-opening polymerisation (rROP) and post- polymerisation microparticle synthesis (using the optimised solvent evaporation technique detailed in Chapter 2). The successful encapsulation of ABM into P(MDO-co-VAc) microparticles is reported and compared to encapsulation into PVAc microparticles. In Chapter 7, the synthesis of poly(ω-pentadecalactone) (PPDL) microparticles using the optimised single oil-in-water emulsion technique (Chapter 2) is reported. Investigation into the synthesis and degradation of films prepared from random copolymers of PPDL and poly(ɛ- caprolactone) (PCL) is described. An attempt at polymerisation-induced self-assembly (PISA) using block copolymers of PPDL and poly(ɛ-decalactone) (PeDL) is demonstrated. In chapter 8, a general summary of Chapters 2-7 is presented and key findings and conclusions highlighted. Chapter 9 provides the experimental methods used throughout this thesis and Chapter 10 provides supporting degradation studies for Chapter 3 and 4

Effects of depth and overgrowth of ephemeral macroalgae on a remote subtidal NE Atlantic eelgrass (Zostera marina) community

We conducted a short-term field sampling complemented with time integrating stable isotope analysis to holistically investigate status and ecological interactions in a remote NE Atlantic Zostera marina meadow. We found high nutrient water concentrations, large biomass of fast-growing, ephemeral macroalgae, low abundance, and biodiversity of epifauna and a food web with thornback ray (Raja clavata) as intermediate and cod (Gadus morhua) as top predator. We observed no variation with increasing depth (3.5-11 m) except for decreasing shoot density and biomass of Zostera and macroalgae. Our results indicate that the Finnoya Zostera ecosystem is eutrophicated. During the past three to four decades, nutrients from aquaculture have steadily increased to reach 75% of anthmpogenic input while the coastal top predator cod has decreased by 50%. We conclude that bottom-up regulation is a predominant driver of change since top-down regulation is generally weak in low density and exposed Zostera ecosystems such as Finnoya.Peer reviewe

Environmentally relevant concentrations of titanium dioxide nanoparticles pose negligible risk to marine microbes.

Nano-sized titanium dioxide (nTiO ) represents the highest produced nanomaterial by mass worldwide and, due to its prevalent industrial and commercial use, it inevitably reaches the natural environment. Previous work has revealed a negative impact of nTiO upon marine phytoplankton growth, however, studies are typically carried out at concentrations far exceeding those measured and predicted to occur in the environment currently. Here, a series of experiments were carried out to assess the effects of both research-grade nTiO and nTiO extracted from consumer products upon the marine dominant cyanobacterium, , and natural marine communities at environmentally relevant and supra-environmental concentrations ( , 1 μg L to 100 mg L ). Cell declines observed in cultures were associated with the extensive aggregation behaviour of nTiO in saline media and the subsequent entrapment of microbial cells. Hence, higher concentrations of nTiO particles exerted a stronger decline of cyanobacterial populations. However, within natural oligotrophic seawater, cultures were able to recover over time as the nanoparticles aggregated out of solution after 72 h. Subsequent shotgun proteomic analysis of cultures exposed to environmentally relevant concentrations confirmed minimal molecular features of toxicity, suggesting that direct physical effects are responsible for short-term microbial population decline. In an additional experiment, the diversity and structure of natural marine microbial communities showed negligible variations when exposed to environmentally relevant nTiO concentrations ( , 25 μg L ). As such, the environmental risk of nTiO towards marine microbial species appears low, however the potential for adverse effects in hotspots of contamination exists. In future, research must be extended to consider any effect of other components of nano-enabled product formulations upon nanomaterial fate and impact within the natural environment

Mutation-independent Allele-Specific Editing by CRISPR-Cas9, a Novel Approach to Treat Autosomal Dominant Disease

CRISPR-Cas9 provides a tool to treat autosomal dominant disease by non-homologous end joining (NHEJ) gene disruption of the mutant allele. In order to discriminate between wild-type and mutant alleles, Streptococcus pyogenes Cas9 (SpCas9) must be able to detect a single nucleotide change. Allele-specific editing can be achieved by using either a guide-specific approach, in which the missense mutation is found within the guide sequence, or a protospacer-adjacent motif (PAM)-specific approach, in which the missense mutation generates a novel PAM. While both approaches have been shown to offer allele specificity in certain contexts, in cases where numerous missense mutations are associated with a particular disease, such as TGFBI (transforming growth factor β-induced) corneal dystrophies, it is neither possible nor realistic to target each mutation individually. In this study, we demonstrate allele-specific CRISPR gene editing independent of the disease-causing mutation that is capable of achieving complete allele discrimination, and we propose it as a targeting approach for autosomal dominant disease. Our approach utilizes natural variants in the target region that contain a PAM on one allele that lies in cis with the causative mutation, removing the constraints of a mutation-dependent approach. Our innovative patient-specific guide design approach takes into account the patient’s individual genetic make-up, allowing on- and off-target activity to be assessed in a personalized manner