Oxidative dehydrogenation of ethane to ethylene over LiCl/MnOx/PC catalysts

The catalytic stability of LiCl/MnOx/PC catalyst have been investigated, the deactivation mechanism was discussed. The experimental results show that ethane conversion decreases and ethylene selectivity keeps about 90% as reaction time increases. The main deactivation reasons of LiCl/MnOx/PC catalyst for oxidative dehydrogenation of ethane (ODHE) to ethylene are the transition of active species Mn2O3 to MnO species and the loss of arrive component Cl in catalyst. instead of ethane with FCC tailed-gas, the stability of LiCl/MnOx/PC catalyst has been largely improved.

Estudo da suscetibilidade aos antibióticos em isolados de Enterobacteriaceae provenientes de suiniculturas Portuguesas

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

Caracterização da estrutura populacional de isolados de Escherichia coli provenientes de suiniculturas de produção intensiva e extensiva de Portugal

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

Nutrition or Detoxification: Why Bats Visit Mineral Licks of the Amazonian Rainforest

Many animals in the tropics of Africa, Asia and South America regularly visit so-called salt or mineral licks to consume clay or drink clay-saturated water. Whether this behavior is used to supplement diets with locally limited nutrients or to buffer the effects of toxic secondary plant compounds remains unclear. In the Amazonian rainforest, pregnant and lactating bats are frequently observed and captured at mineral licks. We measured the nitrogen isotope ratio in wing tissue of omnivorous short-tailed fruit bats, Carollia perspicillata, and in an obligate fruit-eating bat, Artibeus obscurus, captured at mineral licks and at control sites in the rainforest. Carollia perspicillata with a plant-dominated diet were more often captured at mineral licks than individuals with an insect-dominated diet, although insects were more mineral depleted than fruits. In contrast, nitrogen isotope ratios of A. obscurus did not differ between individuals captured at mineral lick versus control sites. We conclude that pregnant and lactating fruit-eating bats do not visit mineral licks principally for minerals, but instead to buffer the effects of secondary plant compounds that they ingest in large quantities during periods of high energy demand. These findings have potential implications for the role of mineral licks for mammals in general, including humans.

On the Relationship Between File Sizes, Transport Protocols, and Self-Similar Network Traffic

Recent measurements of local-area and wide-area traffic have shown that network traffic exhibits variability at a wide range of scales self-similarity. In this paper, we examine a mechanism that gives rise to self-similar network traffic and present some of its performance implications. The mechanism we study is the transfer of files or messages whose size is drawn from a heavy-tailed distribution. We examine its effects through detailed transport-level simulations of multiple TCP streams in an internetwork. First, we show that in a "realistic" client/server network environment i.e., one with bounded resources and coupling among traffic sources competing for resources the degree to which file sizes are heavy-tailed can directly determine the degree of traffic self-similarity at the link level. We show that this causal relationship is not significantly affected by changes in network resources (bottleneck bandwidth and buffer capacity), network topology, the influence of cross-traffic, or the distribution of interarrival times. Second, we show that properties of the transport layer play an important role in preserving and modulating this relationship. In particular, the reliable transmission and flow control mechanisms of TCP (Reno, Tahoe, or Vegas) serve to maintain the long-range dependency structure induced by heavy-tailed file size distributions. In contrast, if a non-flow-controlled and unreliable (UDP-based) transport protocol is used, the resulting traffic shows little self-similar characteristics: although still bursty at short time scales, it has little long-range dependence. If flow-controlled, unreliable transport is employed, the degree of traffic self-similarity is positively correlated with the degree of throttling at the source. Third, in exploring the relationship between file sizes, transport protocols, and self-similarity, we are also able to show some of the performance implications of self-similarity. We present data on the relationship between traffic self-similarity and network performance as captured by performance measures including packet loss rate, retransmission rate, and queueing delay. Increased self-similarity, as expected, results in degradation of performance. Queueing delay, in particular, exhibits a drastic increase with increasing self-similarity. Throughput-related measures such as packet loss and retransmission rate, however, increase only gradually with increasing traffic self-similarity as long as reliable, flow-controlled transport protocol is used.

To Queue or Not to Queue: When Queueing is Better Than Timesharing in a Distributed System

We examine the question of whether to employ the first-come-first-served (FCFS) discipline or the processor-sharing (PS) discipline at the hosts in a distributed server system. We are interested in the case in which service times are drawn from a heavy-tailed distribution, and so have very high variability. Traditional wisdom when task sizes are highly variable would prefer the PS discipline, because it allows small tasks to avoid being delayed behind large tasks in a queue. However, we show that system performance can actually be significantly better under FCFS queueing, if each task is assigned to a host based on the task's size. By task assignment, we mean an algorithm that inspects incoming tasks and assigns them to hosts for service. The particular task assignment policy we propose is called SITA-E: Size Interval Task Assignment with Equal Load. Surprisingly, under SITA-E, FCFS queueing typically outperforms the PS discipline by a factor of about two, as measured by mean waiting time and mean slowdown (waiting time of task divided by its service time). We compare the FCFS/SITA-E policy to the processor-sharing case analytically; in addition we compare it to a number of other policies in simulation. We show that the benefits of SITA-E are present even in small-scale distributed systems (four or more hosts). Furthermore, SITA-E is a static policy that does not incorporate feedback knowledge of the state of the hosts, which allows for a simple and scalable implementation.

Task Assignment in a Distributed System: Improving Performance by Unbalancing Load

We consider the problem of task assignment in a distributed system (such as a distributed Web server) in which task sizes are drawn from a heavy-tailed distribution. Many task assignment algorithms are based on the heuristic that balancing the load at the server hosts will result in optimal performance. We show this conventional wisdom is less true when the task size distribution is heavy-tailed (as is the case for Web file sizes). We introduce a new task assignment policy, called Size Interval Task Assignment with Variable Load (SITA-V). SITA-V purposely operates the server hosts at different loads, and directs smaller tasks to the lighter-loaded hosts. The result is that SITA-V provably decreases the mean task slowdown by significant factors (up to 1000 or more) where the more heavy-tailed the workload, the greater the improvement factor. We evaluate the tradeoff between improvement in slowdown and increase in waiting time in a system using SITA-V, and show conditions under which SITA-V represents a particularly appealing policy. We conclude with a discussion of the use of SITA-V in a distributed Web server, and show that it is attractive because it has a simple implementation which requires no communication from the server hosts back to the task router.

Generating Good Degree Distributions for Sparse Parity Check Codes using Oracles

Fast forward error correction codes are becoming an important component in bulk content delivery. They fit in naturally with multicast scenarios as a way to deal with losses and are now seeing use in peer to peer networks as a basis for distributing load. In particular, new irregular sparse parity check codes have been developed with provable average linear time performance, a significant improvement over previous codes. In this paper, we present a new heuristic for generating codes with similar performance based on observing a server with an oracle for client state. This heuristic is easy to implement and provides further intuition into the need for an irregular heavy tailed distribution.

Scheduling Flows with Unknown Sizes: Approximate Analysis

Previous studies have shown that giving preferential treatment to short jobs helps reduce the average system response time, especially when the job size distribution possesses the heavy-tailed property. Since it has been shown that the TCP flow length distribution also has the same property, it is natural to let short TCP flows enjoy better service inside the network. Analyzing such discriminatory system requires modification to traditional job scheduling models since usually network traffic managers do not have detailed knowledge about individual flows such as their lengths. The Multi-Level (ML) queue, proposed by Kleinrock, can b e used to characterize such system. In an ML queueing system, the priority of a flow is reduced as the flow stays longer. We present an approximate analysis of the ML queueing system to obtain a closed-form solution of the average system response time function for general flow size distributions. We show that the response time of short flows can be significantly reduced without penalizing long flows.

Differentiated Control of Web Traffic: A Numerical Analysis

Internet measurements show that the size distribution of Web-based transactions is usually very skewed; a few large requests constitute most of the total traffic. Motivated by the advantages of scheduling algorithms which favor short jobs, we propose to perform differentiated control over Web-based transactions to give preferential service to short web requests. The control is realized through service semantics provided by Internet Traffic Managers, a Diffserv-like architecture. To evaluate the performance of such a control system, it is necessary to have a fast but accurate analytical method. To this end, we model the Internet as a time-shared system and propose a numerical approach which utilizes Kleinrock's conservation law to solve the model. The numerical results are shown to match well those obtained by packet-level simulation, which runs orders of magnitude slower than our numerical method.

Connection Scheduling in Web Servers

Under high loads, a Web server may be servicing many hundreds of connections concurrently. In traditional Web servers, the question of the order in which concurrent connections are serviced has been left to the operating system. In this paper we ask whether servers might provide better service by using non-traditional service ordering. In particular, for the case when a Web server is serving static files, we examine the costs and benefits of a policy that gives preferential service to short connections. We start by assessing the scheduling behavior of a commonly used server (Apache running on Linux) with respect to connection size and show that it does not appear to provide preferential service to short connections. We then examine the potential performance improvements of a policy that does favor short connections (shortest-connection-first). We show that mean response time can be improved by factors of four or five under shortest-connection-first, as compared to an (Apache-like) size-independent policy. Finally we assess the costs of shortest-connection-first scheduling in terms of unfairness (i.e., the degree to which long connections suffer). We show that under shortest-connection-first scheduling, long connections pay very little penalty. This surprising result can be understood as a consequence of heavy-tailed Web server workloads, in which most connections are small, but most server load is due to the few large connections. We support this explanation using analysis.

Epidemiology and comparative analysis of Yersinia in Ireland

Yersiniosis is an acute or chronic enteric zoonosis caused by enteropathogenic Yersinia species. Although yersiniosis is predominantly associated with gastroenteric forms of infection, extraintestinal forms are often reported from the elderly or patients with predisposing factors. Yersiniosis is often reported in countries with cold and mild climates (Northern and Central Europe, New Zealand and North of Russian Federation). The Irish Health Protection Surveillance Centre (HPSC) currently records only 3-7 notified cases of yersiniosis per year. At the same time pathogenic Yersinia enterocolitica is recovered from pigs (main source of pathogenic Y. enterocolitica) at the levels similar to that observed in Yersinia endemic countries. Introduction of Yersinia selective culture procedures may increase Yersinia isolation rates. To establish whether the small number of notifications of human disease was an underestimate due to lack of specific selective culture for Yersinia we carried out a prospective culture study of faecal samples from outpatients with diarrhoea, with additional culture of appendix and throat swabs. Higher levels of anti-Yersinia seroprevalence than yersiniosis notification rates in endemic countries suggests that most yersiniosis cases are unrecognised by culture. Subsequently, in addition to a prospective culture study of clinical specimens, we carried out serological screening of Irish blood donors and environmental screening of human sewage. Pathogenic Yersinia strains were not isolated from 1,189 faeces samples, nor from 297 throat swabs, or 23 appendix swabs. This suggested that current low notification rates in Ireland are not due to the lack of specific Yersinia culture procedures. Molecular screening detected a wider variety of Y. enterocolitica-specific targets in pig slurry than in human sewage. A serological survey for antibodies against Yersinia YOP (Yersinia Outer Proteins) proteins in Irish blood donors found antibodies in 25%, with an age-related trend to increased seropositivity, compatible with the hypothesis that yersiniosis may have been more prevalent in Ireland in the recent past. Y. enterocolitica is a heterogeneous group of microorganisms that comprises strains with different degree of pathogenicity. Although non-pathogenic Y. enterocolitica lack conventional virulence factors, these strains can be isolated from patients with diarrhoea. Insecticidal Toxin Complex (ITC) and Cytolethal Distending Toxins can potentially contribute to the virulence of non-pathogenic Y. enterocolitica in the absence of other virulence factors. We compared distribution of ITC and CDT loci among pathogenic and non-pathogenic Y. enterocolitica. Additionally, to demonstrate potential pathogenicity of non-pathogenic Y. enterocolitica we compared their virulence towards Galleria mellonella larvae (a non-mammalian model of human bacterial infections) with the virulence of highly and mildly pathogenic Y. enterocolitica strains. Surprisingly, virulence of pathogenic and non-pathogenic Y. enterocolitica in Galleria mellonella larvae observed at 37°C did not correlate with their pathogenic potential towards humans. Comparative phylogenomic analysis detects predicted coding sequences (CDSs) that define host-pathogen interactions and hence providing insights into molecular evolution of bacterial virulence. Comparative phylogenomic analysis of microarray data generated in Y. enterocolitica strains isolated in the Great Britain from humans with diarrhoea and domestic animals revealed high genetic heterogeneity of these species. Because of the extensive human, animal and food exchanges between the UK and Ireland the objective of this study was to gain further insight into genetic heterogeneity and relationships among clinical and non-clinical Y. enterocolitica strains of various pathogenic potential isolated in Ireland and Great Britain. No evidence of direct transfer of strains between the two countries was found.

Development of food ingredients for modulation of glycemia

Starches are a source of digestible carbohydrate and are frequently used in formulated food products in the presence of other carbohydrates, proteins and fat. This thesis explored the effect of addition of neutral (Konjac glucomannan) or charged (milk proteins) polymers on the physical characteristics and digestion kinetics of waxy maize starch. The aim was to identify mechanisms to modulate the pasting properties and subsequent susceptibility to amylolytic digestion. Addition of αs- or β-caseinate protein fractions to waxy maize starch restricted granular swelling during gelatinisation, increasing granule integrity. It was shown that, while β-caseinate can adsorb to starch granules during pasting, αscaseinate can be absorbed into maize starch granules. The resultant effect was a reduction in granule size after heating, more intact granules and a subsequent decrease in starch digestion in vitro as determined by analysis of reducing sugars. The ability of αs-caseinate to reduce the level of amylolytic digestion was confirmed through in vivo pig (Teagasc, Moorepark) and human (University of Surrey, UK) trials. The scope of the thesis extended to the development of a new automated cell for attachment to a rheometer to measure digestion kinetics of starch-protein mixtures. In conclusion, the thesis offers new approaches to modulation of the physical characteristics of unmodified starch during gelatinisation and suggests that the type of protein and/or polysaccharide used in starch-based food systems may influence the ability of the food to modulate glycemia. This is an important consideration in the design of foods with positive health benefits.

Assessment of dietary background exposure of the Irish adult population to dioxins and PCBs particularly taking into account additional exposure due to the 2008 Irish dioxin food contamination incident

Irish monitoring data on PCDD/Fs, DL-PCBs and Marker PCBs were collated and combined with Irish Adult Food Consumption Data, to estimate dietary background exposure of Irish adults to dioxins and PCBs. Furthermore, all available information on the 2008 Irish pork dioxin food contamination incident was collated and analysed with a view to evaluate any potential impact the incident may have had on general dioxin and PCB background exposure levels estimated for the adult population in Ireland. The average upperbound daily intake of Irish adults to dioxins Total WHO TEQ (2005) (PCDD/Fs & DLPCBs) from environmental background contamination, was estimated at 0.3 pg/kg bw/d and at the 95th percentile at 1 pg/kg bw/d. The average upperbound daily intake of Irish adults to the sum of 6 Marker PCBs from environmental background contamination ubiquitous in the environment was estimated at 1.6 ng/kg bw/d and at the 95th percentile at 6.8 ng/kg bw/d. Dietary background exposure estimates for both dioxins and PCBs indicate that the Irish adult population has exposures below the European average, a finding which is also supported by the levels detected in breast milk of Irish mothers. Exposure levels are below health based guidance values and/or Body Burdens associated with the TWI (for dioxins) or associated with a NOAEL (for PCBs). Given the current toxicological knowledge, based on biomarker data and estimated dietary exposure, general background exposure of the Irish adult population to dioxins and PCBs is of no human health concern. In 2008, a porcine fat sample taken as part of the national residues monitoring programme led to the detection of a major feed contamination incidence in the Republic of Ireland. The source of the contamination was traced back to the use of contaminated oil in a direct-drying feed operation system. Congener profiles in animal fat and feed samples showed a high level of consistency and pinpointed the likely source of fuel contamination to be a highly chlorinated commercial PCB mixture. To estimate additional exposure to dioxins and PCBs due to the contamination of pig and cattle herds, collection and a systematic review of all data associated with the contamination incident was conducted. A model was devised that took into account the proportion of contaminated product reaching the final consumer during the 90 day contamination incident window. For a 90 day period, the total additional exposure to Total TEQ (PCDD/F &DL-PCB) WHO (2005) amounted to 407 pg/kg bw/90d at the 95th percentile and 1911 pg/kg bw/90d at the 99th percentile. Exposure estimates derived for both dioxins and PCBs showed that the Body Burden of the general population remained largely unaffected by the contamination incident and approximately 10 % of the adult population in Ireland was exposed to elevated levels of dioxins and PCBs. Whilst people in this 10 % cohort experienced quite a significant additional load to the existing body burden, the estimated exposure values do not indicate approximation of body burdens associated with adverse health effects, based on current knowledge. The exposure period was also limited in time to approximately 3 months, following the FSAI recall of contaminated meat immediately on detection of the contamination. A follow up breast milk study on Irish first time mothers conducted in 2009/2010 did not show any increase in concentrations compared to the study conducted in 2002. The latter supports the conclusion that the majority of the Irish adult population was not affected by the contamination incident.

Biogas production from novel substrates

Biogas production is the conversion of the organic material into methane (CH4) and carbon dioxide (CO2) under anaerobic conditions. Anaerobic digestion (AD) is widely used in continental and Scandinavian communities as both a waste treatment option and a source of renewable energy. Ireland however lags behind this European movement. Numerous feedstocks exist which could be digested and used to fuel a renewable transport fleet in Ireland. An issue exists with the variety of feedstocks; these need to be assessed and quantified to ascertain their potential resource and application to AD. From literature the ideal C:N ratio is between 25 and 30:1. Low levels of C:N (<15) can lead to problems with ammonia inhibition. Within the digester a plentiful supply of nutrients and a balanced C:N is required for stable performance. Feedstocks were sampled from a range of over 100 different substrates in Ireland including for first, second and third generation feedstocks. The C:N ranged from 81:1 (Winter Oats) to 7:1 (Silage Effluent). The BMP yields were recorded ranging from 38 ± 2.0 L CH4 kg−1 VS for pig slurry (weaning pigs) to 805 ± 57 L CH4 kg−1 VS for used cooking oil (UCO). However the selection of the best preforming feedstock in terms of C:N ratio or BMP yield alone is not sufficiently adequate. A total picture has to be created which includes C:N ratio, BMP yield, harvest yield and availability. Potential feedstocks which best meet these requirements include for Grass silage, Milk processing waste (MPW) and Saccharina latissima. MPW has a potential of meeting over 6 times the required energy for Ireland’s 2020 transport in energy targets. S. Latissima recorded a yield of over 10,000 GJ ha-1 yr-1 which out ranks traditional second generation biofuels by a factor of more than 4.