Analyses of hydrocarbon gases and sulphate in sediments from the King George Basin, Antarctica

Thermogenic hydrocarbons, formed by the thermal alteration of organic matter, are encountered in several piston core stations in the King George Basin, Anatarctica. These hemipelagic sediments are being deposited in an area of active hydrothermalism, associated with the back-arc spreading in the Bransfield Strait. The lateral extent of sediments infiltrated by the hydrothermally influenced interstitial fluids is characterized by basalt diapiric intrusions and is delineated by an acoustically turbid zone in the sediments of the eastern part of the basin. Iron-sulphide-bearing veins and fractures cut across the sediment in several cores; they appear to be conduits for flow of hydrothermally altered fluids. These zones have the highest C2+ and ethene contents. The thermogenic hydrocarbons have molecular C1/(C2 + C3) ratios typically < 50 and delta13CH4 values between -38? and -48?, indicating an organic source which has undergone strong thermal stress. Several sediment cores also have mixed gas signatures, which indicate the presence of substantial amounts of bacterial gas, predominantly methane. Hydrocarbon generation in the King George Basin is thought to be a local phenomenon, resulting from submarine volcanism with temperatures in the range 70-150°C. There are no apparent seepages of hydrocarbons into the water column, and it is not believed that significant accumulation of thermogenic hydrocarbons reside in the basin.

Radiopacity and Chemical resistance of Elastomer-Barium sulphate nanocomposites

The Human race of our century is in gluttonous search for novel engineering products which led to a skyrocketed progress in research and fabrication of filled polymers. Recently, a big window has been opened up for speciality polymers especially elastomers with promising properties. Among the many reasons why rubbers are widely used in the process industries, three are considered as important. Firstly, rubbers operate in a variety of environments and possess usable ranges of deformity and durability and can be exploited through suitable and more or less conventional equipment design principles. Secondly, rubber is an eminently suitable construction material for protection against corrosion in the chemical plant and equipment against various corrosive chemicals as, acids and alkalies and if property tailored, can shield ionising radiations as X-rays and gamma rays in medical industry, with minimum maintenance lower down time, negligible corrosion and a preferred choice for aggressive corroding and ionising environment. Thirdly, rubber can readily and hastily, and at a relatively lower cost, be converted into serviceable products, having intricate shapes and dimensions. In a century’s gap, large employment of flexible polymer materials in the different segments of industry has stimulated the development of new materials with special properties, which paved its way to the synthesis of various nanoscale materials. At nano scale, one makes an entry into a world where multidisciplinary sciences meet and utilises the previously unapproached infinitesimal length scale, having dimension which measure upto one billionth of a meter, to create novel properties. The nano fillers augment the elastomers properties in an astonishing fashion due to their multifunctional nature and unprecedented properties have been exhibited by these polymer-nanocomposites just to beat the shortcomings of traditional micro composites. The current research aims to investigate the possibility of using synthesised nano barium sulphate for fabricating elastomer-based nanocomposites and thereby imparting several properties to the rubber. In this thesis, nano materials, their synthesis, structure, properties and applications are studied. The properties of barium sulphate like chemical resistance and radiopacity have been utilized in the present study and is imparted to the elastomers by preparing composites.

Safety and Efficacy of Intravenous Colistin in Neonates With Culture Proven Sepsis

Background: Although it is well described among adults, intravenous colistin use and its associated toxicities in newborns are poorly understood. Objectives: We present our experience of efficacy and safety of intravenous colistin in the treatment of sepsis in term and preterm neonates. Patients and Methods: The records of neonates who received colistin between January 2013 and February 2014 were retrospectively reviewed. All neonates with culture proven nosocomial infections due to multidrug resistant organisms and treated continuously with colistin for more than 72 hours were included in the study. Results: Patients were evaluated for clinical and microbiological response to the drug and its and side effects. Twelve newborn infants with mean 31.8 ± 3.5 weeks gestational age and median 1482 (810 - 3200) gram birth weight were included. 11/12 (91.7%) patients showed microbiological clearance with intravenous colistin. One patient who had recurrent cerebrospinal fluid positive culture was treated with intraventricular colistin. The major side effects observed was hyponatremia and hypokalemia in 2 (16.6%) patients, all infants required magnesium supplementation. Conclusions: Intravenous colistin administration appears to be safe and efficacious for multidrug-resistant gram-negative infections in neonates, including preterm infants. However, we believe that large prospective controlled studies are needed to confirm its efficacy and safety in neonates.

New particle formation and growth at a remote, sub-tropical coastal location

A month-long intensive measurement campaign was conducted in March/April 2007 at Agnes Water, a remote coastal site just south of the Great Barrier Reef on the east coast of Australia. Particle and ion size distributions were continuously measured during the campaign. Coastal nucleation events were observed in clean, marine air masses coming from the south-east on 65% of the days. The events usually began at ~10:00 local time and lasted for 1-4 hrs. They were characterised by the appearance of a nucleation mode with a peak diameter of ~10 nm. The freshly nucleated particles grew within 1-4 hrs up to sizes of 20-50 nm. The events occurred when solar intensity was high (~1000 W m-2) and RH was low (~60%). Interestingly, the events were not related to tide height. The volatile and hygroscopic properties of freshly nucleated particles (17-22.5 nm), simultaneously measured with a volatility-hygroscopicity-tandem differential mobility analyser (VH-TDMA), were used to infer chemical composition. The majority of the volume of these particles was attributed to internally mixed sulphate and organic components. After ruling out coagulation as a source of significant particle growth, we conclude that the condensation of sulphate and/or organic vapours was most likely responsible for driving particle growth during the nucleation events. We cannot make any direct conclusions regarding the chemical species that participated in the initial particle nucleation. However, we suggest that nucleation may have resulted from the photo-oxidation products of unknown sulphur or organic vapours emitted from the waters of Hervey Bay, or from the formation of DMS-derived sulphate clusters over the open ocean that were activated to observable particles by condensable vapours emitted from the nutrient rich waters around Fraser Island or Hervey Bay. Furthermore, a unique and particularly strong nucleation event was observed during northerly wind. The event began early one morning (08:00) and lasted almost the entire day resulting in the production of a large number of ~80 nm particles (average modal concentration during the event was 3200 cm-3). The Great Barrier Reef was the most likely source of precursor vapours responsible for this event.

Water uptake of aerosols with a focus on seeded aerosols and instrumentation techniques

This thesis focuses on the volatile and hygroscopic properties of mixed aerosol species. In particular, the influence organic species of varying solubility have upon seed aerosols. Aerosol studies were conducted at the Paul Scherrer Institut Laboratory for Atmospheric Chemistry (PSI-LAC, Villigen, Switzerland) and at the Queensland University of Technology International Laboratory for Air Quality and Health (QUT-ILAQH, Brisbane, Australia). The primary measurement tool employed in this program was the Volatilisation and Hygroscopicity Tandem Differential Mobility Analyser (VHTDMA - Johnson et al. 2004). This system was initially developed at QUT within the ILAQH and was completely re-developed as part of this project (see Section 1.4 for a description of this process). The new VHTDMA was deployed to the PSI-LAC where an analysis of the volatile and hygroscopic properties of ammonium sulphate seeds coated with organic species formed from the photo-oxidation of á-pinene was conducted. This investigation was driven by a desire to understand the influence of atmospherically prevalent organics upon water uptake by material with cloud forming capabilities. Of particular note from this campaign were observed influences of partially soluble organic coatings upon inorganic ammonium sulphate seeds above and below their deliquescence relative humidity (DRH). Above the DRH of the seed increasing the volume fraction of the organic component was shown to reduce the water uptake of the mixed particle. Below the DRH the organic was shown to activate the water uptake of the seed. This was the first time this effect had been observed for á-pinene derived SOA. In contrast with the simulated aerosols generated at the PSI-LAC a case study of the volatile and hygroscopic properties of diesel emissions was undertaken. During this stage of the project ternary nucleation was shown, for the first time, to be one of the processes involved in formation of diesel particulate matter. Furthermore, these particles were shown to be coated with a volatile hydrophobic material which prevented the water uptake of the highly hygroscopic material below. This result was a first and indicated that previous studies into the hygroscopicity of diesel emission had erroneously reported the particles to be hydrophobic. Both of these results contradict the previously upheld Zdanovksii-Stokes-Robinson (ZSR) additive rule for water uptake by mixed species. This is an important contribution as it adds to the weight of evidence that limits the validity of this rule.

Multi-criteria ranking and source apportionment of fine particulate matter in Brisbane, Australia

This paper reports the application of multicriteria decision making techniques, PROMETHEE and GAIA, and receptor models, PCA/APCS and PMF, to data from an air monitoring site located on the campus of Queensland University of Technology in Brisbane, Australia and operated by Queensland Environmental Protection Agency (QEPA). The data consisted of the concentrations of 21 chemical species and meteorological data collected between 1995 and 2003. PROMETHEE/GAIA separated the samples into those collected when leaded and unleaded petrol were used to power vehicles in the region. The number and source profiles of the factors obtained from PCA/APCS and PMF analyses were compared. There are noticeable differences in the outcomes possibly because of the non-negative constraints imposed on the PMF analysis. While PCA/APCS identified 6 sources, PMF reduced the data to 9 factors. Each factor had distinctive compositions that suggested that motor vehicle emissions, controlled burning of forests, secondary sulphate, sea salt and road dust/soil were the most important sources of fine particulate matter at the site. The most plausible locations of the sources were identified by combining the results obtained from the receptor models with meteorological data. The study demonstrated the potential benefits of combining results from multi-criteria decision making analysis with those from receptor models in order to gain insights into information that could enhance the development of air pollution control measures.

Intercomparison study of six HTDMAs: results and recommendations

We report on an inter-comparison of six different hygroscopicity tandem differential mobility analysers (HTDMAs). These HTDMAs are used worldwide in laboratories and in field campaigns to measure the water uptake of aerosol particles and were never intercompared. After an investigation of the different design of the instruments with their advantages and inconveniencies, the methods for calibration, validation and analysis are presented. Measurements of nebulised ammonium sulphate as well as of secondary organic aerosol generated from a smog chamber were performed. Agreement and discrepancies between the instrument and to the theory are discussed, and final recommendations for a standard instrument are given, as a benchmark for laboratory or field experiments to ensure a high quality of HTDMA data.

Establishment of a mouse model of colitis and its use to evaluate the anti-inflammatory effects of two ghrelin peptides

Ghrelin is a gut-brain peptide hormone that induces appetite, stimulates the release of growth hormone, and has recently been shown to ameliorate inflammation. Recent studies have suggested that ghrelin may play a potential role in inflammation-related diseases such as inflammatory bowel diseases (IBD). A previous study with ghrelin in the TNBS mouse model of colitis demonstrated that ghrelin treatment decreased the clinical severity of colitis and inflammation and prevented the recurrence of disease. Ghrelin may be acting at the immunological and epithelial level as the ghrelin receptor (GHSR) is expressed by immune cells and intestinal epithelial cells. The current project investigated the effect of ghrelin in a different mouse model of colitis using dextran sodium sulphate (DSS) – a luminal toxin. Two molecular weight forms of DSS were used as they give differing effects (5kDa and 40kDa). Ghrelin treatment significantly improved clinical colitis scores (p=0.012) in the C57BL/6 mouse strain with colitis induced by 2% DSS (5kDa). Treatment with ghrelin suppressed colitis in the proximal colon as indicated by reduced accumulative histopathology scores (p=0.03). Whilst there was a trend toward reduced scores in the mid and distal colon in these mice this did not reach significance. Ghrelin did not affect histopathology scores in the 40kDa model. There was no significant effect on the number of regulatory T cells or TNF-α secretion from cultured lymph node cells from these mice. The discovery of C-terminal ghrelin peptides, for example, obestatin and the peptide derived from exon 4 deleted proghrelin (Δ4 preproghrelin peptide) have raised questions regarding their potential role in biological functions. The current project investigated the effect of Δ4 peptide in the DSS model of colitis however no significant suppression of colitis was observed. In vitro epithelial wound healing assays were also undertaken to determine the effect of ghrelin on intestinal epithelial cell migration. Ghrelin did not significantly improve wound healing in these assays. In conclusion, ghrelin treatment displays a mild anti-inflammatory effect in the 5kDa DSS model. The potential mechanisms behind this effect and the disparity between these results and those published previously will be discussed.

An application of near-infrared and mid-infrared spectroscopy to the study of natural halotrichites : halotrichite, apjohnite and wupatkiite

Near-infrared (NIR) and Fourier transform infrared (FTIR) spectroscopy have been used to determine the mineralogical character of isomorphic substitutions for Mg2+ by divalent transition metals Fe, Mn, Co and Ni in natural halotrichite series. The minerals are characterised by d-d transitions in NIR region 12000-7500 cm-1. NIR spectrum of halotrichite reveals broad feature from 12000 to 7500 cm-1 with a splitting of two bands resulting from ferrous ion transition 5T2g ® 5Eg. The presence of overtones of OH- fundamentals near 7000 cm-1 confirms molecular water in the mineral structure of the halotrichite series. The appearance of the most intense peak at around 5132 cm-1 is a common feature in the three minerals and is derived from combination of OH- vibrations of water molecules and 2 water bending modes. The influence of cations like Mg2+, Fe2+, Mn2+, Co2+, Ni2+ shows on the spectra of halotrichites. Especially wupatkiite-OH stretching vibrations in which bands are distorted conspicuously to low wave numbers at 3270, 2904 and 2454 cm-1. The observation of high frequency 2 mode in the infrared spectrum at 1640 cm-1 indicates coordination of water molecules is strongly hydrogen bonded in natural halotrichites. The splittings of bands in 3 and 4 (SO4)2- stretching regions may be attributed to the reduction of symmetry from Td to C2v for sulphate ion. This work has shown the usefulness of NIR spectroscopy for the rapid identification and classification of the halotrichite minerals.

Spectroscopy of selected copper group minerals : chalcophyllite and chenevixite-implications for hydrogen bonding

NIR and IR spectroscopy has been applied for detection of chemical species and the nature of hydrogen bonding in arsenate complexes. The structure and spectral properties of copper(II) arsenate minerals chalcophyllite and chenevixite are compared with copper(II) sulphate minerals devilline, chalcoalumite and caledonite. Split NIR bands in the electronic spectrum of two ranges 11700-8500 cm-1 and 8500-7200 cm-1 confirm distortion of octahedral symmetry for Cu(II) in the arsenate complexes. The observed bands with maxima at 9860 and 7750 cm-1 are assigned to Cu(II) transitions 2B1g ® 2B2g and 2B1g ® 2A1g. Overlapping bands in the NIR region 4500-4000 cm-1 is the effect of multi anions OH-, (AsO4)3- and (SO4)2-. The observation of broad and diffuse bands in the range 3700-2900 cm-1 confirms strong hydrogen bonding in chalcophyllite relative to chenevixite. The position of the water bending vibrations indicates the water is strongly hydrogen bonded in the mineral structure. The strong absorption feature centred at 1644 cm-1 in chalcophyllite indicates water is strongly hydrogen bonded in the mineral structure. The H2O-bending vibrations shift to low wavenumbers in chenevixite and an additional band observed at 1390 cm-1 is related to carbonate impurity. The characterisation of IR spectra by ν3 antisymmetric stretching vibrations of (SO4)2- and (AsO4)3 ions near 1100 and 800 cm-1 respectively is the result of isomorphic substitution for arsenate by sulphate in both the minerals of chalcophyllite and chenevixite.