Phase Equilibria of Binary and Ternary Systems Containing ILs, Dodecane, and Cyclohexanecarboxylic Acid

This paper reports both the binary and ternary phase behavior of ionic liquids for extracting cyclohexanecarboxylic acid (CCA) from dodecane. This system is a model for the extraction of acids representative of naphthenic acids found in crude oils. In order to develop an effective ternary liquid-liquid extraction system the preliminary selection of ionic liquids was based on CCA miscibility and the dodecane immiscibility with selected ILs. A wide range of ILs based on different cations, anions, cation alkyl-chain length, as well as the effect of temperature on the overall fluid phase behavior is reported. Factors such as variation of cation group, anion effect, alkyl-chain length, and temperature all impact the extraction to various degrees. The largest effects were found to be the lipophilicity of the IL cation and the co-ordination ability of the anion. While CCA capacity increased with lipophilicity of the cation, as did the dodecane. Highly coordinating anions such as trifluoroacetate and triflate demonstrated that highly efficient extraction could be obtained producing favorable tie-lines in the ternary phase diagram. Overall, this study demonstrates that ILs can selectively extract acids from hydrocarbon streams and offers possible treatment solutions for problems associated with the processing of high acid crude oils.

The sympathetic release test: a test used to assess thermoregulation and autonomic control of blood flow

When a subject is heated, the stimulation of temperature-sensitive nerve endings in the skin, and the raising of the central body temperature, results in the reflex release of sympathetic vasoconstrictor tone in the skin of the extremities, causing a measurable temperature increase at the site of release. In the sympathetic release test, the subject is gently heated by placing the feet and calves in a commercially available foot warming pouch or immersing the feet and calves in warm water and wrapping the subject in blankets. Skin blood flow is estimated from measurements of skin temperature in the fingers. Normally skin temperature of the fingers is 65-75 degrees F in cool conditions (environmental temperature: 59-68 degrees F) and rises to 85-95 degrees F during body heating. Deviations in this pattern may mean that there is abnormal sympathetic vasoconstrictor control of skin blood flow. Abnormal skin blood flow can substantially impair an individual's ability to thermoregulate and has important clinical implications. During whole body heating, the skin temperature from three different skin sites is monitored and oral temperature is monitored as an index of core temperature. Students determine the fingertip temperature at which the reflex release of sympathetic activity occurs and its maximal attainment, which reflects the vasodilating capacity of this cutaneous vascular bed. Students should interpret typical sample data for certain clinical conditions (Raynaud's disease, peripheral vascular disease, and postsympathectomy) and explain why there may be altered skin blood flow in these disorders.

Quantitative Analysis of Fault and Fracture Systems and their Impact on Groundwater Flow in Irish Bedrock Aquifers

Fault and fracture systems are the most important store and pathway for groundwater in Ireland’s bedrock aquifers, either directly as conductive flow structures, or indirectly as the locus for the development of dolomitised limestone and karst. This article presents the preliminary results of a study involving the quantitative analysis of fault and fracture systems in the broad range of Irish bedrock types and a consideration of their impact on groundwater flow. The principal aims of the project are to develop generic conceptual models for different fault/fracture systems in different lithologies and at different depths, and to link them to observed groundwater behaviour. Here we briefly describe the geometrical characteristics of the main post-Devonian fault/fracture systems controlling groundwater flow from field observations at outcrops, quarries and mines. The structures range from Lower Carboniferous normal faults through to Variscan-related faults and veins, with the most recent structures including Tertiary strike-slip faults and ubiquitous uplift-related joint systems. The geometrical characteristics of different fault/fracture systems combined with observations of groundwater behaviour in both quarry and mine localities, can be linked to general flow and transport conceptualisations of Irish fractured bedrock. Most importantly they also provide a basis for relating groundwater flow to particular fault/fracture systems and their expression with depth and within different lithological sequences, as well as their regional variability.

Storage of sediment-associated nutrients and contaminants in river channel and floodplain systems

Samples of fine-grained channel bed sediment and overbank floodplain deposits were collected along the main channels of the Rivers Aire (and its main tributary, the River Calder) and Swale, in Yorkshire, UK, in order to investigate downstream changes in the storage and deposition of heavy metals (Cr, Cu, Pb, Zn), total P and the sum of selected PCB congeners, and to estimate the total storage of these contaminants within the main channels and floodplains of these river systems. Downstream trends in the contaminant content of the <63 μm fraction of channel bed and floodplain sediment in the study rivers are controlled mainly by the location of the main sources of the contaminants, which varies between rivers. In the Rivers Aire and Calder, the contaminant content of the <63 μm fraction of channel bed and floodplain sediment generally increases in a downstream direction, reflecting the location of the main urban and industrialized areas in the middle and lower parts of the basin. In the River Swale, the concentrations of most of the contaminants examined are approximately constant along the length of the river, due to the relatively unpolluted nature of this river. However, the Pb and Zn content of fine channel bed sediment decreases downstream, due to the location of historic metal mines in the headwaters of this river, and the effect of downstream dilution with uncontaminated sediment. The magnitude and spatial variation of contaminant storage and deposition on channel beds and floodplains are also controlled by the amount of <63 μm sediment stored on the channel bed and deposited on the floodplain during overbank events. Consequently, contaminant deposition and storage are strongly influenced by the surface area of the floodplain and channel bed. Contaminant storage on the channel beds of the study rivers is, therefore, generally greatest in the middle and lower reaches of the rivers, since channel width increases downstream. Comparisons of the estimates of total storage of specific contaminants on the channel beds of the main channel systems of the study rivers with the annual contaminant flux at the catchment outlets indicate that channel storage represents <3% of the outlet flux and is, therefore, of limited importance in regulating that flux. Similar comparisons between the annual deposition flux of specific contaminants to the floodplains of the study rivers and the annual contaminant flux at the catchment outlet, emphasise the potential importance of floodplain deposition as a conveyance loss. In the case of the River Aire the floodplain deposition flux is equivalent to between ca. 2% (PCBs) and 36% (Pb) of the outlet flux. With the exception of PCBs, for which the value is ≅0, the equivalent values for the River Swale range between 18% (P) and 95% (Pb). The study emphasises that knowledge of the fine-grained sediment delivery system operating in a river basin is an essential prerequisite for understanding the transport and storage of sediment-associated contaminants in river systems and that conveyance losses associated with floodplain deposition exert an important control on downstream contaminant fluxes and the fate of such contaminants. © 2003 Elsevier Science Ltd. All rights reserved.

Mechanism of Alizarin Red S and Methylene Blue Biosorption onto Olive Stone: Isotherm study in Single and Binary Systems

The biosorption process of anionic dye Alizarin Red S (ARS) and cationic dye methylene blue (MB) as a function of contact time, initial concentration and solution pH onto olive stone (OS) biomass has been investigated. Equilibrium biosorption isotherms in single and binary systems and kinetics in batch mode were also examined. The kinetic data of the two dyes were better described by the pseudo second-order model. At low concentration, ARS dye appeared to follow a two-step diffusion process, while MB dye followed a three-step diffusion process. The biosorption experimental data for ARS and MB dyes were well suited to the Redlich-Peterson isotherm. The maximum biosorption of ARS dye, qmax = 16.10 mg/g, was obtained at pH 3.28 and the maximum biosorption of MB dye, qmax = 13.20 mg/g, was observed at basic pH values. In the binary system, it was indicated that the MB dye diffuses firstly inside the biosorbent particle and occupies the biosorption sites forming a monodentate complex and then the ARS dye enters and can only bind to untaken sites; forms a tridentate complex with OS active sites.

A realistic evaluation of track and trigger systems and acute care training for early recognition and treatment of deteriorating ward-based patients: research protocol.

Aim The aim of the study is to evaluate factors that enable or constrain the implementation and service delivery of early warnings systems or acute care training in practice. Background To date there is limited evidence to support the effectiveness of acute care initiatives (early warning systems, acute care training, outreach) in reducing the number of adverse events (cardiac arrest, death, unanticipated Intensive Care admission) through increased recognition and management of deteriorating ward based patients in hospital [1-3]. The reasons posited are that previous research primarily focused on measuring patient outcomes following the implementation of an intervention or programme without considering the social factors (the organisation, the people, external influences) which may have affected the process of implementation and hence measured end-points. Further research which considers the social processes is required in order to understand why a programme works, or does not work, in particular circumstances [4]. Method The design is a multiple case study approach of four general wards in two acute hospitals where Early Warning Systems (EWS) and Acute Life-threatening Events Recognition and Treatment (ALERT) course have been implemented. Various methods are being used to collect data about individual capacities, interpersonal relationships and institutional balance and infrastructures in order to understand the intended and unintended process outcomes of implementing EWS and ALERT in practice. This information will be gathered from individual and focus group interviews with key participants (ALERT facilitators, nursing and medical ALERT instructors, ward managers, doctors, ward nurses and health care assistants from each hospital); non-participant observation of ward organisation and structure; audit of patients' EWS charts and audit of the medical notes of patients who deteriorated during the study period to ascertain whether ALERT principles were followed. Discussion & progress to date This study commenced in January 2007. Ethical approval has been granted and data collection is ongoing with interviews being conducted with key stakeholders. The findings from this study will provide evidence for policy-makers to make informed decisions regarding the direction for strategic and service planning of acute care services to improve the level of care provided to acutely ill patients in hospital. References 1. Esmonde L, McDonnell A, Ball C, Waskett C, Morgan R, Rashidain A et al. Investigating the effectiveness of Critical Care Outreach Services: A systematic review. Intensive Care Medicine 2006; 32: 1713-1721 2. McGaughey J, Alderdice F, Fowler R, Kapila A, Mayhew A, Moutray M. Outreach and Early Warning Systems for the prevention of Intensive Care admission and death of critically ill patients on general hospital wards. Cochrane Database of Systematic Reviews 2007, Issue 3. www.thecochranelibrary.com 3. Winters BD, Pham JC, Hunt EA, Guallar E, Berenholtz S, Pronovost PJ (2007) Rapid Response Systems: A systematic review. Critical Care Medicine 2007; 35 (5): 1238-43 4. Pawson R and Tilley N. Realistic Evaluation. London; Sage: 1997

On Passive Intermodulation Test of Analog and Digital Systems

This paper presents initial results of evaluating suitability of the conventional two-tone CW passive intermodulation (PIM) test for characterization of modulated signal distortion by passive nonlinearities in base station antennas and RF front-end. A comprehensive analysis of analog and digitally modulated waveforms in the transmission lines with weak distributed nonlinearity has been performed using the harmonic balance analysis and X-parameters in Advanced Design System (ADS) simulator. The nonlinear distortion metrics used in the conventional two-tone CW PIM test have been compared with the respective spectral metrics applied to the modulated waveforms, such as adjacent channel power ratio (ACPR) and error vector magnitude (EVM). It is shown that the results of two-tone CW PIM tests are consistent with the metrics used for assessment of signal integrity of both analog and digitally modulated waveforms.

A validated UPLC–MS/MS method for the surveillance of ten aquatic biotoxins in European brackish and freshwater systems

Over the past few decades, there has been an increased frequency and duration of cyanobacterial Harmful Algal Blooms (HABs) in freshwater systems globally. These can produce secondary metabolites called cyanotoxins, many of which are hepatotoxins, raising concerns about repeated exposure through ingestion of contaminated drinking water or food or through recreational activities such as bathing/ swimming. An ultra-performance liquid chromatography tandem mass spectrometry (UPLC–MS/MS) multi-toxin method has been developed and validated for freshwater cyanotoxins; microcystins-LR, -YR, -RR, -LA, -LY and -LF, nodularin, cylindrospermopsin, anatoxin-a and the marine diatom toxin domoic acid. Separation was achieved in around 9 min and dual SPE was incorporated providing detection limits of between 0.3 and 5.6 ng/L of original sample. Intra- and inter-day precision analysis showed relative
standard deviations (RSD) of 1.2–9.6% and 1.3–12.0% respectively. The method was applied to the analysis of aquatic samples (n = 206) from six European countries. The main class detected were the hepatotoxins; microcystin-YR (n = 22), cylindrospermopsin (n = 25), microcystin-RR (n = 17), microcystin-LR (n = 12), microcystin-LY (n = 1), microcystin-LF (n = 1) and nodularin (n = 5). For microcystins, the levels detected ranged from 0.001 to 1.51 mg/L, with two samples showing combined levels above the guideline set by the WHO of 1 mg/L for microcystin-LR. Several samples presented with multiple toxins indicating the potential for synergistic effects and possibly enhanced toxicity. This is the first published pan European survey of freshwater bodies for multiple biotoxins, including two identified for the first time; cylindrospermopsin in Ireland and nodularin in Germany, presenting further incentives for improved monitoring and development of strategies to mitigate human exposure.

People and places: Understanding geographical accuracy in administrative data from the census and healthcare systems

Administrative systems such as health care registration are of increasing importance in providing information for statistical, research, and policy purposes. There is thus a pressing need to understand better the detailed relationship between population characteristics as recorded in such systems and conventional censuses. This paper explores these issues using the unique Northern Ireland Longitudinal Study (NILS). It takes the 2001 Census enumeration as a benchmark and analyses the social, demographic and spatial patterns of mismatch with the health register at individual level. Descriptive comparison is followed by multivariate and multilevel analyses which show that approximately 25% of individuals are reported to be in different addresses and that age, rurality, education, and housing type are all important factors. This level of mismatch appears to be maintained over time, as earlier migrants who update their address details are replaced by others who have not yet done so. In some cases, apparent mismatches seem likely to reflect complex multi-address living arrangements rather than data error.

Automatic information and safety systems for driving assistance

O objeto principal desta tese é o estudo de algoritmos de processamento e representação automáticos de dados, em particular de informação obtida por sensores montados a bordo de veículos (2D e 3D), com aplicação em contexto de sistemas de apoio à condução. O trabalho foca alguns dos problemas que, quer os sistemas de condução automática (AD), quer os sistemas avançados de apoio à condução (ADAS), enfrentam hoje em dia. O documento é composto por duas partes. A primeira descreve o projeto, construção e desenvolvimento de três protótipos robóticos, incluindo pormenores associados aos sensores montados a bordo dos robôs, algoritmos e arquitecturas de software. Estes robôs foram utilizados como plataformas de ensaios para testar e validar as técnicas propostas. Para além disso, participaram em várias competições de condução autónoma tendo obtido muito bons resultados. A segunda parte deste documento apresenta vários algoritmos empregues na geração de representações intermédias de dados sensoriais. Estes podem ser utilizados para melhorar técnicas já existentes de reconhecimento de padrões, deteção ou navegação, e por este meio contribuir para futuras aplicações no âmbito dos AD ou ADAS. Dado que os veículos autónomos contêm uma grande quantidade de sensores de diferentes naturezas, representações intermédias são particularmente adequadas, pois podem lidar com problemas relacionados com as diversas naturezas dos dados (2D, 3D, fotométrica, etc.), com o carácter assíncrono dos dados (multiplos sensores a enviar dados a diferentes frequências), ou com o alinhamento dos dados (problemas de calibração, diferentes sensores a disponibilizar diferentes medições para um mesmo objeto). Neste âmbito, são propostas novas técnicas para a computação de uma representação multi-câmara multi-modal de transformação de perspectiva inversa, para a execução de correcção de côr entre imagens de forma a obter mosaicos de qualidade, ou para a geração de uma representação de cena baseada em primitivas poligonais, capaz de lidar com grandes quantidades de dados 3D e 2D, tendo inclusivamente a capacidade de refinar a representação à medida que novos dados sensoriais são recebidos.

Monte Carlo studies of phase transitions and adsorption : application to n-6 Lennard-Jones, C60 and zeolite systems

The solid-fluid transition properties of the n - 6 Lennard-Jones system are studied by means of extensive free energy calculations. Different values of the parameter n which regulates the steepness of the short-range repulsive interaction are investigated. Furthermore, the free energies of the n < 12 systems are calculated using the n = 12 system as a reference. The method relies on a generalization of the multiple histogram method that combines independent canonical ensemble simulations performed with different Hamiltonians and computes the free energy difference between them. The phase behavior of the fullerene C60 solid is studied by performing NPT simulations using atomistic models which treat each carbon in the molecule as a separate interaction site with additional bond charges. In particular, the transition from an orientationally frozen phase at low temperatures to one where the molecules are freely rotating at higher temperatures is studied as a function of applied pressure. The adsorption of molecular hydrogen in the zeolite NaA is investigated by means of grand-canonical Monte Carlo, in a wide range of temperatures and imposed gas pressures, and results are compared with available experimental data. A potential model is used that comprises three main interactions: van der Waals, Coulomb and induced polarization by the permanent electric field in the zeolite.