<p dir="ltr">Acoustic guitar soundboard material selection is based on selective evaluations that have been developed over centuries. These traditional practices are not conducive to the guitar industry we experience today because the supply of traditionally acceptable soundboard wood has decreased greatly. The purpose of this research was to develop an objective wood selection metric to determine the sound quality of an acoustic guitar’s soundboard. The metric would replace the subjective evaluations traditionally used to select materials for acoustic guitar soundboards.</p><p dir="ltr">The acoustic properties of sound radiation coefficient, material’s speed of sound, resonance and damping and the material properties of longitudinal and radial elastic modulus, density, and specific modulus were used in an attempt to construct a material selection metric. These variables were selected because the literature review revealed that these were the most critical variables in determining sound quality. The gaps in the literature were testing and analyzing samples that represented the true dimensions of an acoustic guitar soundboard blank and forming the metric. The literature revealed that the previous experimental studies did not have the appropriate test sample dimensions that correspond to the test samples evaluated by the subjective methods.</p><p dir="ltr">The methodology was carried out by using the objective testing counterparts to the subjective assessments found in the literature review. Instrumented hammer tap testing collected data to determine damping and resonance frequencies. A three-point static bending test collected data for longitudinal and radial elastic modulus. Mass and dimension measurements were recorded to calculate density. Calculations were done to compute the acoustic properties and specific modulus of the test samples. These variables were put into a table and underwent statistical analysis in the form of predictor correlation and logistical regression. The experimental variables were modeled against the subjective evaluation of an expert on the usability of the test samples.</p><p dir="ltr">Statistical analysis proved that the dataset did not show any significant separation between “good” or “bad” test samples or a significant correlation between the usability of the test sample and the variables in the dataset. The methodology did not produce an objective material selection metric to determine the sound quality of an acoustic guitar’s soundboard. Future research should include a wider range of measured frequencies and the collection of time domain data.</p>

<p dir="ltr">The goal of this thesis is to develop a method of evaluating long-term IAQ performance of an industrial facility and use machine-learning to model the relationship between critical air pollutants and the facility’s HVAC systems and processes. The facility under study for this thesis is an electroplating manufacturer. The air pollutants at this facility that were studied were particulate matter, total-volatile organic compounds, and carbon-dioxide. Upon sensor installation, seven “zones” were identified to isolate areas of the plant for measurement and analysis. A statistical review of the long-term data highlighted how this facility performed in terms of compliance. Their gaseous pollutants were well within regulation. Particulate matter, however, was found to be a pressing issue. PM10 was outside of compliance more than 15% of the time in five out of seven of the zones of study. Some zones were out of compliance up to 80% of the total collection period. The six pollutants that met these criteria were deemed critical and moved on to machine learning modeling. Our model of best fit for each pollutant used a gaussian process regression model, which fits best for non-linear rightly skewed datasets. The performance of each of our models was deemed significant. Every model had at least a regression coefficient of 0.935 and above for both validation and testing. The maximum average error was 12.64 ug.m^3, which is less than 10% of the average PM10 concentration. Through our modeling, we were able to study how HVAC and production played a role in particulate matter presence for each zone. Exhaust systems of the west side of the plant were found to be insufficient at removing particulates from their facility. Overall, the methods developed in this thesis project were able to meet the goal of analyzing IAQ compliance, modeling critical pollutants using machine learning, and identifying a relationship between these pollutants and an industrial facility’s HVAC and production systems.</p>

<p dir="ltr">There is a growing trend towards the development of parsimonious surrogate models for studying physical phenomena. While they typically offer less accuracy, these models bypass the computational costs of numerical methods, usually by multiple orders of magnitude, allowing statistical applications such as sensitivity analysis, stochastic treatments, parametric problems, and uncertainty quantification. Researchers have explored generalized surrogate frameworks leveraging Gaussian processes, various basis function expansions, support vector machines, and neural networks. Dynamical fields, represented through time-dependent partial differential equation, pose a particular hardship for existing frameworks due to their high dimensional representation, and possibly multi-scale solutions.</p><p dir="ltr">In this work, we present a novel architecture for solving time-dependent partial differential equations using co-ordinate neural networks and time-marching updates through hyper-networks. We show that it provides a temporally meshed and spatially mesh-free solution which are causally coherent as justified through a theoretical treatment of Lie groups. We showcase results on some benchmark problems in computational physics while discussing their performance against similar physics-informed approaches like physics-informed DeepOnets and Physics informed neural networks.</p>

Introduction Oral delivery of proteins faces numerous challenges due to their enzymatic susceptibility and instability in the gastrointestinal tract. In recent years, the polyelectrolyte complexes have been explored for their ability to complex protein and protect them against chemical and enzymatic degradation. However, most of the conventional binary polyelectrolyte complexes (PECs) are formed by polycations which are associated with toxicity and non-specific bio-interactions. The aim of this thesis was to prepare a series of ternary polyelectrolyte complexes (APECs) by introduction of a polyanion in the binary complexes to alleviate the aforementioned limitations. Method Eight non-insulin loaded ternary complexes (NIL APECs) were spontaneously formed upon mixing a polycation [polyallylamine (PAH), palmitoyl grafted-PAH (Pa2.5), dimethylamino-1-naphthalenesulfonyl grafted-PAH (Da10) or quaternised palmitoyl-PAH (QPa2.5)] with a polyanion [dextran sulphate (DS) or polyacrylic acid (PAA)] at 2:1 ratio, in the presence of ZnSO4 (4μM). A model protein i.e., insulin was added to a polycation, prior to addition of a polyanion and ZnSO4 to form eight insulin loaded (IL) APECs. PECs were used as a control to compare APECs. The complexes were characterised by dynamic light scattering (DLS) and transmission electron microscope (TEM). In vitro stability of the complexes was investigated at pH (1.2-7.4), temperature (25˚C, 37˚C and 45˚C) and ionic strength (NaCl-68mM, 103mM and 145mM). Insulin complexation efficiency was assessed by using bovine insulin ELISA assay kit. The in vitro cytotoxicity was investigated on CaCo2 and J774 cells by MTT (3-4,5 dimethyl thialzol2,5 diphenyl tetrazolium bromide) assay. All complexes were evaluated for their haemocompatibility by using haemolysis assay, oxidative stress by reactive oxygen species (ROS) assay and immunotoxicity by in vitro and in vivo cytokine generation assay. The potential of the uptake of complexes across CaCo2 cells was determined by flow cytometry and fluorescent microscopy. The underlying mechanism of transport of complexes was determined by TEER measurement, assessment of FITC-Dextran and insulin transport across CaCo2 cells. 15 Results NIL QPa2.5 APECs (except IL QPa2.5-DS) exhibited larger hydrodynamic sizes (228-468nm) than all other APECs, due to the presence of bulky quaternary ammonium moieties. QPa2.5 APECs exhibited lower insulin association efficiency (≤40%) than other APECs (≥55%) due to a competition between the polyanion and insulin for QPa2.5 leading to reduced association of insulin in the complexes. DS based APECs generally offered higher insulin association efficiency (≥75%) than PAA based APECs (≤55%) due to higher molecular weight (6-10kDa) of DS. In comparison to other complexes, Pa2.5 PECs and APECs were more stable at varying temperature, ionic strength and pH due to the presence of long palmitoyl alkyl chain (C16) which reduced the chain flexibility and provided stronger hydrophobic association. The cytotoxicity of polycations on CaCo2 and J774 cells is rated as PAH>Da10=Pa2.5>QPa2.5. The introduction of PAA in Pa2.5 and Da10 brought most significant improvement in IC50 i.e., 14 fold and 16 fold respectively on CaCo2 cells; 9.3 fold and 3.73 fold respectively on J774 cells. In comparison to other complexes, Da10 (8mgml-1) induced higher haemolytic activity (~37%) due to a higher hydrophobic load of 10 percent mole grafting of dansyl pendants. The entire range of APECs displayed ≤12% ROS generation by the CaCo2 cells. The degree of in vitro TNFα production (QPa2.5≥Da10≥Pa2.5=PAH) and in vitro IL-6 generation (QPa2.5≥Pa2.5=PAH≥Da10) by J774 cells established an inverse relationship of cytotoxicity with the cytokine generation. Similar to MTT data, the introduction of PAA in APECs brought more significant reduction in in vitro cytokine secretion than DS based APECs. Pa2.5-PAA brought the most significant reduction in both in vitro and in vivo cytokine generation. All the formulations were able to significantly reduce original TEER, however did not demonstrate appreciable paracellular permeation of a hydrophilic macromolecular tracer of paracellular transport i.e., FITC Dextran. The uptake study revealed internalisation of APECs predominantly by a transcellular route. Transcellular uptake of IL QPa2.5 (≤73%), IL QPa2.5-DS (67%) was higher than their NIL counterparts, whereas the uptake of NIL Pa2.5 (≤89%), NIL Pa2.5-PAA (42%) was higher than their IL counterparts. Conclusion In essence, amphiphilic APECs have shown polyanion dependent ability to reduce polycation associated toxicity and they are able to facilitate transcellular uptake of insulin across CaCo2 cells.

Surface functionalised silica materials have been prepared, followed by the extensive testing of their ability to remove metal ions from aqueous solutions. Modifications include ligand attachment and polymer grafting from the silica surface whilst the metals tested range from first row transition metals right through to the lanthanides and actinides. Characterisation of the materials produced has been of paramount importance for the understanding of the modification process and this is also extensively discussed. Atom transfer radical polymerisation (ATRP) has been used as the primary polymerisation method. Following polymerisation of 2-hydroxyethyl methacrylate (HEMA), post functionalisation was attempted. However, this was found to cause severe cross-linking and all attempts to attach ligands to this failed. Nonetheless, this process was transferred to grafting from silica surfaces and a novel approach to the characterisation of this material was implemented. (3-aminopropyl) triethoxysilane (APTES) was reacted with multiple forms of silica, primarily ZEOprep silica (average particle size 71.48 πm) and fumed silica (0.007 μm). This produced an amine coated surface to which 2-bromoisobutyryl bromide (BIBB) was attached, providing the required surface for radical polymerisation to proceed with a selected monomer. Solid State Nuclear Magnetic Resonance (SSNMR) has been utilised as the major characterisation technique for each step, leading to significant understanding of how this occurs. Thermogravimetric Analysis (TGA) and elemental analysis has supported this method at each stage whilst also enabling one to calculate the moles of APTES present, per gram of APTES-functionalised silica. For the ZEOprep silica this was calculated to be at up to 1.51 x 10-3 mol g-1 and for the fumed silica 1.63 x 10-3 mol g-1. As well as testing the selective nature of these materials, solutions of individual ions and radionuclides were used to measure the effectiveness of the materials for a specific ion. Rd values for these metals ions including solutions of Co(II), Ni(II), Cu(II), Cd2+, Eu(III) and [UO2]2+ have reached values ranging from 7.49 x 104 mL g-1 to as high as 2.17 x 109 mL g-1. These values are regarded as outstanding by other groups that have reported similar results and these are discussed in the report. This range includes values that were observed when competing Na+ and Ca2+ ions were present at 0.5 % and 1 % (w/w). pH testing was also investigated with the materials using a solution of europium ions to determine the most effective range and this was found to fall between pH 4 and 5. X-ray Photoelectron Spectroscopy (XPS) has been utilised to help gain an understanding of the binding between Cu(II) ions and APTES, suggesting that copper ions bind with oxygen atoms closer to the silica surface as well as the nitrogen atoms at the end of the ligand. Meanwhile STEM (Scanning Transmission Electron Microscope) has been used to show how effectively the surface area of the material is used by imaging the europium ions over a sample of APTES-functionalised fumed silica. Ligands and polymers have been focussed on to build a catalogue of functional materials and this has been achieved in collaboration with PhosphonicS Ltd. The most significant finding from these selective investigations was that uranyl ions were found to be the most readily removed. Cu(II) and Eu(III) ions were also removed relatively effectively whilst Co(II), Ni(II), Zn2+ and Cd2+ proved the most challenging but certainly not impossible. [UO2]2+ concentrations were reduced from 17.1 ppm to 1.6 ppm after 4 weeks with use of the ligand SEA (2-aminoethyl sulfide ethyl silica), even with six other metal ions present at similar initial concentrations and a starting pH of 4.67 by adding just 50 mg of the material to a 45 mL solution.

This study analyses the nature and implementation of electronic commerce in order to identify possible problems for taxation and pinpoint those problems which may be relevant to South Africa. Solutions suggested by certain countries and institutions are evaluated for possible implementation in South Africa. The study suggests that although current taxation legislation in South Africa is apP'icable to electronic commerce transactions it is not sufficient to cater effectively for this type of business. The conclusion reached Is that international co-operation is essential in finding solutions. A number of recommendations are made regarding aspects of South African taxation legislation which need to be clarified through policy decisions. Title of / Taxation / M.Comm.

Current strategies for designing biomaterials involve creating materials and interfaces that interact with biomolecules, cells and tissues.  This thesis aims to investigate several bioactive surfaces, such as nanocrystalline diamond (NCD), hydroxyapatite (HA) and single crystalline titanium dioxide, in terms of material synthesis, surface functionalization and characterization. Although cochlear implants (CIs) have been proven to be clinically successful, the efficiency of these implants still needs to be improved. A CI typically only has 12-20 electrodes while the ear has approximately 3400 inner hair cells. A type of micro-textured NCD surface that consists of micrometre-sized nail-head-shaped pillars was fabricated. Auditory neurons showed a strong affinity for the surface of the NCD pillars, and the technique could be used for neural guidance and to increase the number of stimulation points, leading to CIs with improved performance. Typical transparent ceramics are fabricated using pressure-assisted sintering techniques. However, the development of a simple energy-efficient production method remains a challenge. A simple approach to fabricating translucent nano-ceramics was developed by controlling the morphology of the starting ceramic particles. Translucent nano-ceramics, including HA and strontium substituted HA, could be produced via a simple filtration process followed by pressure-less sintering. Furthermore, the application of such materials as a window material was investigated. The results show that MC3T3 cells could be observed through the translucent HA ceramic for up to 7 days. The living fluorescent staining confirmed that the MC3T3 cells were visible throughout the culture period. Single crystalline rutile possesses in vitro bioactivity, and the crystalline direction affects HA formation. The HA growth on (001), (100) and (110) faces was investigated in a simulated body fluid in the presence of fibronectin (FN) via two different processes. The HA layers on each face were analysed using different characterization techniques, revealing that the interfacial energies could be altered by the pre-adsorbed FN, which influenced HA formation. In summary, micro textured NCD, and translucent HA and FN functionalized single crystalline rutile, and their interactions with cells and biomimetic HA were studied. The results showed that controlled surface properties are important for enhancing a material’s biological performance.

Thesis (MscAgric (Viticulture and Oenology))--University of Stellenbosch, 2007. / The rapid expansion of the world wine industry has increased the pressure on wine producers to produce high quality, distinguishable wines. The use of sensory evaluation alone as a tool to distinguish between wines is limited by its subjective nature. Chemical characterisation using analytical methods and data analysis techniques are increasingly being used in conjunction with sensory analysis for comprehensive profiling of wine. Analytical chemistry and chemometric techniques are important and inextricable parts of the chemical characterisation of wine. Through this process insight into the inherent composition of wines, be it in a general sense or related to a particular wine category is gained. Data generated during chemical characterisation are typically compiled into electronic databases. The application of such information towards wine quality control includes the establishment of industry benchmarks and authentication. The current project is part of The South African Young Wine Aroma Project, a long term research initiative funded by the South African Wine Industry with the ultimate aim to establish a comprehensive, up-to-date, database of the volatile composition of young wines. The data generated during this thesis represent the first contribution towards realising this ambition. Three clearly defined aims were set for this project, the first of which is the chemical characterisation of South African young wines in terms of selected volatile and non-volatile compounds and Fourier transform infrared spectra, with particular focus on the volatile composition. FTMIR spectra are information rich and non-specific instrumental signals that could provide invaluable information of the inherent composition of the wines. The second aim is the evaluation of the analytical methods used to generate the data and in the last instance, the optimisation of FTMIR spectroscopy for rapid quantification of major wine parameters and volatile compounds. The concentrations of 27 volatile compounds in South African young wines were determined by gas chromatography coupled to flame ionisation detection (GC-FID) using liquid-liquid extraction of the analytes. Wine samples of the 2005 and 2006 vintages produced from six of the most important cultivars in the South African wine industry, namely Sauvignon blanc, Chardonnay, Pinotage, Cabernet Sauvignon, Merlot and Shiraz were used. The producing cellars were from four major South African wine producing regions, namely Stellenbosch, Paarl, Robertson and Worcester. The data captured made a significant contribution to the establishment of the Aroma Project Database. Univariate statistics showed wide variations in the chemical composition of the wines. Red wines were generally characterised by high levels of higher alcohols and white wines by high levels of esters. Most of the differences between vintages were cultivar dependent and phenological differences between cultivars were suggested as a possible cause. Fusel alcohols, iso-acids and esters of fusel alcohols were particularly responsible for differences between red wines. A combination of fatty acids and higher alcohols were responsible for differences between production regions. However, using univariate statistics alone was limited in identifying characteristic features of the chemical composition of the wines. In order to explore the correlations between the volatile components, FTMIR spectra and nonvolatile components the data were further investigated with multivariate data analysis. Principal component analysis was successfully employed to distinguish between wines of different vintages and cultivars. The role of the volatile composition was more influential in the separation of vintage and red wine cultivar groupings than the non-volatile components or the FTMIR spectra. Almost all the individual volatile components contributed to the separation between the vintages and cultivars, thereby highlighting the multivariate nature required to establish the distinguishing features pertaining to each of these categories. The FTMIR spectra and the non-volatile components were more important than the volatile components to characterise the differences between the white cultivars. It was not surprising that both the volatile components and the FTMIR spectra were needed to distinguish between both red and white cultivars simultaneously. It was of interest the full spectrum, including all wavenumbers were required for a powerful classification model. This finding supports the initial expectation that the non-selective but information rich signal captured in the FTMIR spectra is indispensable. No distinction could be made between the production regions, which was not surprising since the wines used in this study was not of guaranteed origin. Furthermore, no clear correlation could be established between the chemical composition or the FTMIR spectra and the quality ratings of the wines. Limitations in the dataset were pointed out that must be taken into account during further investigations in the future. The liquid-liquid extraction method used during the analysis of the volatile components was evaluated for precision, accuracy and robustness. Generally good precision and accuracy were observed. There were slight indications of inconsistencies in the recoveries of analytes between the red and white wine matrices. Certain parameters of the protocol, namely sample volume, solvent volume, sonication temperature and sonication time, were identified as factors that had a major influence on quantification. The results obtained in this study made a major contribution towards establishing this technique for routine GC-FID analysis in our environment. Due to the high sample throughput in wine laboratories, the use of rapid quantitative analytical methods such as FTMIR spectroscopy is becoming increasingly important. Enzymatic-linked spectrophotometric assays and high performance liquid chromatography (HPLC) methods were evaluated for their suitability to serve as reference methods for optimising and establishing FTMIR calibrations for glucose, fructose, malic acid, lactic acid and glycerol. Pigmented and phenolic compounds were identified as sources of interference in the determination of organic acids in red wines with both enzymatic assays and HPLC. The use of fining treatments for the decolourisation of red wine samples was investigated. Activated charcoal was more efficient in terms of colour removal than polyvinyl polypyrrolidone (PVPP), but neither were compatible with the specific enzymatic method used in this study. Solid phase extraction (SPE), a method commonly used during sample clean-up prior to HPLC analysis of organic acids in wine, and PVPP fining were evaluated as sample preparation methods for HPLC analysis to optimise the quantification of organic acids in red wine. Four different types of SPE cartridges were evaluated and the SPE method was optimised in order to recover the maximum amount of organic acids. However, low recoveries, in some instance less than 50%, for the organic acids in wine were reported for the optimised SPE method. In this respect one was the worst. On average, excellent recoveries were observed for the organic acids using the PVPP method that were in excess of 90%. This method therefore provides a very valuable and simple alternative to SPE for sample-cleanup prior to HPLC analysis. One aspect that still needs to be investigated is the reproducibility of the method that should still be optimised. In general, enzymatic analysis was more suitable for the determination of glucose and fructose, while HPLC analysis were more suitable for the quantification of organic acids. Efficient glycerol quantification was observed with both enzymatic and HPLC analysis, although a lower measurement error was observed during the HPLC analysis. Apart from reliable reference methods, successful FTMIR calibrations also rely on the variability present in the reference sample set. The reference sample set used to establish FTMIR calibrations must ideally be representative of the samples that will be analysed in the future. Commercial, or so-called global, FTMIR calibrations for the determination of important wine parameters were evaluated for their compatibility to a South African young wine matrix. The prediction pH, titratable acidity, malic acid, glucose, fructose, ethanol and glycerol could be improved by establishing a brand new FTMIR calibration, thereby clearly indicating that the South African young wine matrices were significantly different from the samples of European origin that were used to establish the commercial calibrations. New preliminary calibration models were established for a young wine sample matrix and were validated using independent test sets. On average the prediction errors were considered sufficient for at least screening purposes. The effect of wavenumber selection was evaluated. Relatively successful models could be established for all the compounds except glucose. Wavenumber selection had an influence on the efficiency of the calibration models. Some models were more effective using a small amount of highly correlated wavenumbers, while others were more effective using larger wavenumber regions. Preliminary FTMIR calibration models for the screening of volatile compound groups in young wines were evaluated. Compound groups were compiled based on chemical similarity and flavour similarity. Good linearity were observed for the “total alcohol”, “total fatty acids”, “esters” models while an interesting polynomial trend was observed for the “total esters” model. Relatively high prediction errors indicated the possibility of spectral interferences, but the models were nevertheless considered suitable for screening purposes. These findings are a valuable contribution to our environment where fermentation flavour profiles must often be examined. The important role sound and validated analytical methods to generate high quality analytical data, and the subsequent application of chemometric techniques to model the data for the purpose of wine characterisation has been thoroughly explored in this study. After a critical evaluation of the analytical methods used in this study, various statistical methods were used to uncover the chemical composition of South African young wines. The use of multivariate data analysis has revealed some limitations in the dataset and therefore it must be said that wine characterisation is not just reliant on sophisticated analytical chemistry and advanced data analytical techniques, but also on high quality sample sets.

The presence of the sea ice diatom biomarker IP25 in Arctic marine sediments has been used in previous studies as a proxy for past spring sea ice occurrence and as an indicator of wider palaeoenvironmental conditions for different regions of the Arctic over various timescales. The current study describes a number of analytical and palaeoceanographic developments of the IP25 sea ice biomarker. First, IP25 was extracted and purified from Arctic marine sediments. This enabled the structure of IP25 to be confirmed and enabled instrumental (GC-MS) calibrations to be carried out so that quantitative measurements could be performed with greater accuracy. Second, palaeo sea ice reconstructions based on IP25 and other biomarkers were carried out for a suite of sub-Arctic areas within the Greenland, Norwegian and Barents Seas, each of which represent contrasting oceanographic and environmental settings. Further, an evaluation of some combined biomarker approaches (e.g. the PIP25 and DIP25 indices) for quantifying and/or refining definitions of sea ice conditions was carried out. Temporally, particular emphasis was placed on the characterisation of sea ice conditions during the Younger Dryas and the Holocene. Some comparisons with other proxies (e.g. foraminifera, IRD) were also made. A study of a sediment core from Andfjorden (69.16˚N, 16.25˚E), northern Norway, provided unequivocal evidence for the occurrence of seasonal sea ice conditions during the Younger Dryas. The onset (ca. 12.9 cal. kyr BP) and end (ca. 11.5 cal. kyr BP) of this stadial were especially clear in this location, while in a study from the Kveithola Trough (74.52˚N, 16.29˚E), western Barents Sea, these transitions were less apparent. This was attributed to the presence of colder surface waters and the occurrence of seasonal sea ice both before and after this stadial at higher latitudes. Some regional differences regarding the severity of the sea ice conditions were also observed, although an overall general picture was proposed, with more severe sea ice conditions during the early-mid Younger Dryas and less sea ice observed during the late Younger Dryas. A shift in the climate towards ice-free conditions was recorded in northern Norway during the early Holocene (ca. 11.5 – 7.2 cal. kyr BP). Milder conditions were also observed during the Holocene in the western Barents Sea, with three main climate periods observed. During the early Holocene (ca. 11.7 – 9.5 cal. kyr BP), the position of the spring ice edge was close to the study area which resulted in high productivity during summers. During the mid-late Holocene (ca. 9.5 – 1.6 cal. kyr BP), sea ice was mainly absent due to an increased influence of Atlantic waters and northward movement of the Polar Front. During the last ca. 1.6 cal. kyr BP, sea ice conditions were similar to those of the present day. In addition to the outcomes obtained from the Norwegian-Barents Sea region, comparison of biomarker and other proxy data from 3 short cores from Kangerdlugssuaq Trough (Denmark Strait/SE Greenland) with historical climate observations allowed the development of a model of sea ice conditions which was then tested for longer time-scales. It is suggested that the IP25 in sediments from this region is likely derived from drift ice carried from the Arctic Ocean via the East Greenland Current and that two main sea surface scenarios have existed over the last ca. 150 yr. From ca. AD 1850 – 1910, near perennial sea ice conditions resulted in very low primary productivity, while from ca. AD 1910 – 1986, local sea ice conditions were less severe with increased drift ice and enhanced primary productivity. This two-component model was subsequently developed to accommodate different sea surface conditions that existed during the retreat of the Greenland Ice Sheet during the deglaciation (ca. 16.3 – 10.9 cal. kyr BP).

Form, mobility, toxicity and the eventual fate of engineered nanomaterials in environmental ecosystems are currently not well defined and are needed to improve risk assessment and legislation. The present study subjected uncoated zinc oxide (ZnO) nanoparticles (30nm and 200nm) and coated silver (Ag) nanoparticles (Paraffin: 3-8nm and citrate/PVP: 50nm) to different ionic strength media and different types of algal/bacterial extracellular-polymeric species (EPS) at long (6 months) and short (2 weeks) timescales. Changes in particle size distribution and stability were examined using a multi-method approach. Sample concentration and sample polydispersity are important factors when selecting techniques. Uncoated ZnO nanoparticles aggregated heavily in water at high concentrations (1000mg/L). However silver nanoparticles (1-10mg/L) remained stable at all ionic strengths and EPS in this study due to the steric component of their coatings. Nano-toxicological experiments involving cyanobacteria S.leopoliensis and green algae C.reinhardtii showed size-dependent toxicity from coated nanosilver particles. Smaller nanoparticles (3-8nm) showed greater dissolution over 72h and greater toxicity to both species than 50nm particles indicating silver ions are an important toxicity mechanism. Nanoparticle coatings were likely important in controlling dissolution levels. Cell viability and production of reactive oxygen species (ROS) were shown to be important mechanisms of toxicity to phycological species. Species specific effects were noted for both silver nanoparticles. EPS from S.leopoliensis were noted to remove ionic silver from suspension and different types of C.reinhardtii EPS were produced when particles underwent different levels of toxic stress indicating that EPS could both affect particle toxicity and be affected by it. This work has demonstrated that coated nanoparticles could remain stable under various ionic strengths and with exposure to algal organic matter for timescales up to 6 months. This could result in adverse effects to aquatic organisms were they to reach environmental systems and is of concern to nanomaterial risk assessors.