Gridded bathymetry from multibeam echosounder EM122 data of the cruise M84/2, off Eregli (2011)

We investigated gas bubble emissions at the Don-Kuban paleo-fan in the northeastern Black Sea regarding their geological setting, quantities as well as spatial and temporal variabilities during three ship expeditions between 2007 and 2011. About 600 bubble-induced hydroacoustic anomalies in the water column (flares) originating from the seafloor above the gas hydrate stability zone (GHSZ) at ~700 m water depth were found. At about 890 m water depth a hydrocarbon seep area named "Kerch seep area" was newly discovered within the GHSZ. We propose locally domed sediments ('mounds') discovered during ultra-high resolution bathymetric mapping with an autonomous underwater vehicle (AUV) to result from gas hydrate accumulation at shallow depths. In situ measurements indicated spatially limited temperature elevations in the shallow sediment likely induced by upward fluid flow which may confine the local GHSZ to a few meters below the seafloor. As a result, gas bubbles are suspected to migrate into near-surface sediments and to escape the seafloor through small-scale faults. Hydroacoustic surveys revealed that several flares originated from a seafloor area of about 1 km**2 in size. The highest flare disappeared in about 350 m water depth, suggesting that the released methane remains in the water column. A methane flux estimate, combining data from visual quantifications during dives with a remotely operated vehicle (ROV) with results from ship-based hydroacoustic surveys and gas analysis revealed that between 2 and 87 x 10**6 mol CH4 yr-1 escaped into the water column above the Kerch seep area. Our results show that the finding of the Kerch seep area represents a so far underestimated type of hydrocarbon seep, which has to be considered in methane budget calculations.

A Bayesian regression approach to assess uncertainty in pollutant wash-off modelling

Due to knowledge gaps in relation to urban stormwater quality processes, an in-depth understanding of model uncertainty can enhance decision making. Uncertainty in stormwater quality models can originate from a range of sources such as the complexity of urban rainfall-runoff-stormwater pollutant processes and the paucity of observed data. Unfortunately, studies relating to epistemic uncertainty, which arises from the simplification of reality are limited and often deemed mostly unquantifiable. This paper presents a statistical modelling framework for ascertaining epistemic uncertainty associated with pollutant wash-off under a regression modelling paradigm using Ordinary Least Squares Regression (OLSR) and Weighted Least Squares Regression (WLSR) methods with a Bayesian/Gibbs sampling statistical approach. The study results confirmed that WLSR assuming probability distributed data provides more realistic uncertainty estimates of the observed and predicted wash-off values compared to OLSR modelling. It was also noted that the Bayesian/Gibbs sampling approach is superior compared to the most commonly adopted classical statistical and deterministic approaches commonly used in water quality modelling. The study outcomes confirmed that the predication error associated with wash-off replication is relatively higher due to limited data availability. The uncertainty analysis also highlighted the variability of the wash-off modelling coefficient k as a function of complex physical processes, which is primarily influenced by surface characteristics and rainfall intensity.

From Polymorph Screening to Dissolution Testing - Solid Phase Analysis during Pharmaceutical Development and Manufacturing

Solid materials can exist in different physical structures without a change in chemical composition. This phenomenon, known as polymorphism, has several implications on pharmaceutical development and manufacturing. Various solid forms of a drug can possess different physical and chemical properties, which may affect processing characteristics and stability, as well as the performance of a drug in the human body. Therefore, knowledge and control of the solid forms is fundamental to maintain safety and high quality of pharmaceuticals. During manufacture, harsh conditions can give rise to unexpected solid phase transformations and therefore change the behavior of the drug. Traditionally, pharmaceutical production has relied on time-consuming off-line analysis of production batches and finished products. This has led to poor understanding of processes and drug products. Therefore, new powerful methods that enable real time monitoring of pharmaceuticals during manufacturing processes are greatly needed. The aim of this thesis was to apply spectroscopic techniques to solid phase analysis within different stages of drug development and manufacturing, and thus, provide a molecular level insight into the behavior of active pharmaceutical ingredients (APIs) during processing. Applications to polymorph screening and different unit operations were developed and studied. A new approach to dissolution testing, which involves simultaneous measurement of drug concentration in the dissolution medium and in-situ solid phase analysis of the dissolving sample, was introduced and studied. Solid phase analysis was successfully performed during different stages, enabling a molecular level insight into the occurring phenomena. Near-infrared (NIR) spectroscopy was utilized in screening of polymorphs and processing-induced transformations (PITs). Polymorph screening was also studied with NIR and Raman spectroscopy in tandem. Quantitative solid phase analysis during fluidized bed drying was performed with in-line NIR and Raman spectroscopy and partial least squares (PLS) regression, and different dehydration mechanisms were studied using in-situ spectroscopy and partial least squares discriminant analysis (PLS-DA). In-situ solid phase analysis with Raman spectroscopy during dissolution testing enabled analysis of dissolution as a whole, and provided a scientific explanation for changes in the dissolution rate. It was concluded that the methods applied and studied provide better process understanding and knowledge of the drug products, and therefore, a way to achieve better quality.

Application of sorbers to mitigate greenhouse gas emissions from land-applied pig litter

Nitrous oxide is the foremost greenhouse gas (GHG)generated by land-applied manures and chemical fertilisers (Australian Government 2013). This research project was part of the National Agricultural Manure Management Program and investigated the potential for sorbers (i.e. specific naturally-occurring minerals) to decrease GHG emissions from spent piggery litter (as well as other manures)applied to soils. The sorbers investigated in this research were vermiculite and bentonite. Both are clays with high cation exchange capacities, of approximately 100–150 cmol/kg Faure 1998). The hypothesis tested in this study was that the sorbers bind ammonium in soil solution thereby suppressing ammonia (NH3)volatilisation and in doing so, slowing the kinetics of nitrate formation and associated nitrous oxide (N2O) emissions. A series of laboratory, glasshouse and field experiments were conducted to assess the sorbers’ effectiveness. The laboratory experiments comprised 64 vessels containing manure and sorber/manure ratios ranging from 1 : 10 to 1 : 1 incorporated into a sandy Sodosol via mixing. The glasshouse trial involved 240 pots comprising manure/sorber incubations placed 5 cm below the soil surface, two soil types (sandy Sodosol and Ferrosol) and two different nitrogen (N) application rates (50 kg N/ha and 150 kg N/ha) with a model plant (kikuyu grass). The field trial consisted of 96, 2 m · 2 m plots on a Ferrosol site with digit grass used as a model plant. Manure/ sorber mixtures were applied in trenches (5 cm below surface) to these plots at increasing sorber levels at anNloading rate of 200 kg/ha. Gas produced in all experiments was plumbed into a purpose-built automated gas analysis (N2O, NH3, CH4, CO2) system. In the laboratory experiments, the sorbers showed strong capacity to decreaseNH3 emissions (up to 80% decrease). Ammonia emissions were close to the detection limit in all treatments in the glasshouse and field trial. In all experiments, considerable N2O decreases (>40%) were achieved by the sorbers. As an example, mean N2O emission decreases from the field trial phase of the project are shown in Fig. 1a. The decrease inGHGemissions brought about by the clays did not negatively impact agronomic performance. Both vermiculite and bentonite resulted in a significant increase in dry matter yields in the field trial (Fig. 1b). Continuing work will optimise the sorber technology for improved environmental and agronomic performance across a range of soils (Vertosol, Dermosol in addition to Ferrosol and Sodosols) and environmental parameters (moisture, temperature, porosity, pH).

Design and fabrication of an automated thermal desorption gas-solid reaction system: Oxidation of ammonia and methanol over YBa2Cu3O7−δ(123) oxide systems

A fully automated, versatile Temperature Programmed Desorption (TDP), Temperature Programmed Reaction (TPR) and Evolved Gas Analysis (EGA) system has been designed and fabricated. The system consists of a micro-reactor which can be evacuated to 10−6 torr and can be heated from 30 to 750°C at a rate of 5 to 30°C per minute. The gas evolved from the reactor is analysed by a quadrupole mass spectrometer (1–300 amu). Data on each of the mass scans and the temperature at a given time are acquired by a PC/AT system to generate thermograms. The functioning of the system is exemplified by the temperature programmed desorption (TPD) of oxygen from YBa2Cu3−xCoxO7 ± δ, catalytic ammonia oxidation to NO over YBa2Cu3O7−δ and anaerobic oxidation of methanol to CO2, CO and H2O over YBa2Cu3O7−δ (Y123) and PrBa2Cu3O7−δ (Pr123) systems.

The Validation of a Two-Dimensional Transient Catalyst Model for Direct Injection Two-Stroke Applications

This paper describes the detailed validation of a computer model designed to simulate the transient light-off in a two-stroke oxidation catalyst. A plug flow reactor is employed to provide measurements of temperature and gas concentration at various radial and axial locations inside the catalyst. These measurements are recorded at discrete intervals during a transient light-off in which the inlet temperature is increased from ambient to 300oC at rates of up to 6oC/sec. The catalyst formulation used in the flow reactor, and its associated test procedures, are then simulated by the computer and a comparison made between experimental readings and model predictions. The design of the computer model to which this validation exercise relates is described in detail in a separate technical paper. The first section of the paper investigates the warm-up characteristics of the substrate and examines the validity of the heat transfer predictions between the wall and the gas in the absence of chemical reactions. The predictions from a typical single-component CO transient light-off test are discussed in the second section and are compared with experimental data. In particular the effect of the temperature ramp on the light-off curve and reaction zone development is examined. An analysis of the C3H6 conversion is given in the third section while the final section examines the accuracy of the light-off curves which are produced when both CO and C3H6 are present in the feed gas. The analysis shows that the heat and mass transfer calculations provided reliable predictions of the warm-up behaviour and post light-off gas concentration profiles. The self-inhibition and cross-inhibition terms in the global rate expressions were also found to be reasonably reliable although the surface reaction rates required calibration with experimental data.

A method for carbon stable isotope analysis of methyl halides and chlorofluorocarbons at pptv concentrations

A pre-concentration system has been validated for use with a gas chromatography/mass spectrometry/isotope ratio mass spectrometer (GC/MS/IRMS) to determine ambient air 13C/12C ratios for methyl halides (MeCl and MeBr) and chlorofluorocarbons (CFCs). The isotopic composition of specific compounds can provide useful information on their atmospheric budgets and biogeochemistry that cannot be ascertained from abundance measurements alone. Although pre-concentration systems have been previously used with a GC/MS/IRMS for atmospheric trace gas analysis, this is the first study also to report system validation tests. Validation results indicate that the pre-concentration system and subsequent separation technologies do not significantly alter the stable isotopic ratios of the target methyl halides, CFC-12 (CCl2F2) and CFC-113 (C2Cl3F3). Significant, but consistent, isotopic shifts of -27.5 to -25.6 do occur within the system for CFC-11 (CCl3F), although the shift is correctible. The method presented has the capacity to separate these target halocarbons from more than 50 other compounds in ambient air samples. Separation allows for the determination of stable carbon isotope ratios of five of these six target trace atmospheric constituents within ambient air for large volume samples (10 L). Representative urban air analyses from Belfast City are also presented which give carbon isotope results similar to published values for 13C/12C analysis of MeCl (-39.1) and CFC-113 (-28.1). However, this is the first paper reporting stable carbon isotope signatures for CFC-11 (-29.4) and CFC-12 (-37.0).

DITRANS - a multi-agent system for integrated diagnosis of power transformers

This paper describes the development and the implementation of a multi-agent system for integrated diagnosis of power transformers. The system is divided in layers which contain a number of agents performing different functions. The social ability and cooperation between the agents lead to the final diagnosis and to other relevant conclusions through integrating various monitoring technologies, diagnostic methods and data sources, such as the dissolved gas analysis.

Caracterização de metabólitos não voláteis da cana-de-açúcar

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The application of neural networks to the analysis of dissolved gases in insulating oil used in transformers

The state of insulating oils used in transformers is determined through the accomplishment of physical-chemical tests, which determine the state of the oil, as well as the chromatography test, which determines possible faults in the equipment. This article concentrate on determining, from a new methodology, a relationship among the variation of the indices obtained from the physical-chemical tests with those indices supplied by the chromatography tests.The determination of the relationship among the tests is accomplished through the application of neural networks. From the data obtained by physical-chemical tests, the network is capable to determine the relationship among the concentration of the main gases present in a certain sample, which were detected by the chromatography tests.More specifically, the proposed approach uses neural networks of perceptron type constituted of multiple layers. After the process of network training, it is possible to determine the existent relationship between the physical-chemical tests and the amount of gases present in the insulating oil.

Effect of remote ischaemic preconditioning in cardiac dysfunction and end-organ injury following cardiac surgery with cardiopulmonary bypass in children: A translational approach investigating clinical outcome and myocardial molecular biology

Congenital heart disease (CHD) is the most common birth defect, causing an important rate of morbidity and mortality. Treatment of CHD requires surgical correction in a significant percentage of cases which exposes patients to cardiac and end organ injury. Cardiac surgical procedures often require the utilisation of cardiopulmonary bypass (CPB), a system that replaces heart and lungs function by diverting circulation into an external circuit. The use of CPB can initiate potent inflammatory responses, in addition a proportion of procedures require a period of aortic cross clamp during which the heart is rendered ischaemic and is exposed to injury. High O2 concentrations are used during cardiac procedures and when circulation is re-established to the heart which had adjusted metabolically to ischaemia, further injury is caused in a process known as ischaemic reperfusion injury (IRI). Several strategies are in place in order to protect the heart during surgery, however injury is still caused, having detrimental effects in patients at short and long term. Remote ischaemic preconditioning (RIPC) is a technique proposed as a potential cardioprotective measure. It consists of exposing a remote tissue bed to brief episodes of ischaemia prior to surgery in order to activate protective pathways that would act during CPB, ischaemia and reperfusion. This study aimed to assess RIPC in paediatric patients requiring CHD surgical correction with a translational approach, integrating clinical outcome, marker analysis, cardiac function parameters and molecular mechanisms within the cardiac tissue. A prospective, single blinded, randomized, controlled trial was conducted applying a RIPC protocol to randomised patients through episodes of limb ischaemia on the day before surgery which was repeated right before the surgery started, after anaesthesia induction. Blood samples were obtained before surgery and at three post-operative time points from venous lines, additional pre and post-bypass blood samples were obtained from the right atrium. Myocardial tissue was resected during the ischaemic period of surgery. Echocardiographic images were obtained before the surgery started after anaesthetic induction and the day after surgery, images were stored for later off line analysis. PICU surveillance data was collected including ventilation parameters, inotrope use, standard laboratory analysis and six hourly blood gas analysis. Pre and post-operative quantitation of markers in blood specimens included cardiac troponin I (cTnI) and B-type natriuretic peptide (BNP), inflammatory mediators including interleukins IL-6, IL-8, IL-10, tumour necrosis factor (TNF-α), and the adhesion molecules ICAM-1 and VCAM-1; the renal marker Cystatin C and the cardiovascular markers asymmetric dymethylarginine (ADMA) and symmetric dymethylarginine (SDMA). Nitric oxide (NO) metabolites and cyclic guanosine monophosphate (cGMP) were measured before and after bypass. Myocardial tissue was processed at baseline and after incubation at hyperoxic concentration during four hours in order to mimic surgical conditions. Expression of genes involved in IRI and RIPC pathways was analysed including heat shock proteins (HSPs), toll like receptors (TLRs), transcription factors nuclear factor κ-B (NF- κ-B) and hypoxia inducible factor 1 (HIF-1). The participation of hydrogen sulfide enzymatic genes, apelin and its receptor were explored. There was no significant difference according to group allocation in any of the echocardiographic parameters. There was a tendency for higher cTnI values and inotropic score in control patients post-operatively, however this was not statistically significant. BNP presented no significant difference according to group allocation. Inflammatory parameters tended to be higher in the control group, however only TNF- α was significantly higher. There was no difference in levels of Cystatin C, NO metabolites, cGMP, ADMA or SDMA. RIPC patients required shorter PICU stay, all other clinical and laboratory analysis presented no difference related to the intervention. Gene expression analysis revealed interesting patterns before and after incubation. HSP-60 presented a lower expression at baseline in tissue corresponding to RIPC patients, no other differences were found. This study provided with valuable descriptive information on previously known and newly explored parameters in the study population. Demographic characteristics and the presence of cyanosis before surgery influenced patterns of activity in several parameters, numerous indicators were linked to the degree of injury suffered by the myocardium. RIPC did not reduce markers of cardiac injury or improved echocardiographic parameters and it did not have an effect on end organ function; some effects were seen in inflammatory responses and gene expression analysis. Nevertheless, an important clinical outcome indicator, PICU length of stay was reduced suggesting benefit from the intervention. Larger studies with more statistical power could determine if the tendency of lower injury and inflammatory markers linked to RIPC is real. The present results mostly support findings of larger multicentre trials which have reported no cardiac benefit from RIPC in paediatric cardiac surgery.