Pilot study of a group clinical supervision model for medical students.

OBJECTIVE: To trial a clinical supervision model with medical students, co-designed by students and clinicians, and evaluate its feasibility, acceptability, and perceived benefits. METHOD: Two clinical supervision groups, one online and one face-to-face, were conducted for six one-hour sessions, over 12 weeks. Clinical supervision was evaluated through mixed methods including attendance levels, focus groups, and quantitative surveys. RESULTS: Thirteen students participated, including one rural and one regional group, each with a clinical supervisor. Attendance was 100%. Students viewed clinical supervision as a safe time for reflection on clinical experiences, validation from senior clinicians and peers, and connection to the medical community. Themes that emerged included strategies to prevent moral injury, self-care, and the need for a trusted clinical supervisor. CONCLUSION: The clinical supervision model received positive medical student evaluations and 100% attendance. This shows promise as an avenue to professionally support medical students as they navigate complex clinical training.

Evacuation characteristics of released airborne TiO2 nanomaterial particles under different ventilation rates in a confined environment.

A specially designed 32 m3 airtight chamber that allows the implementation of various ventilation strategies was utilised to study the evacuation characteristics of airborne sub-micron particles generated from TiO2 nanopowder in a potential indoor accidental release situation. Following the release using a heated line from a nebuliser system, the spatial and temporal variations in particle number concentration were recorded by three condensation particle counters (CPCs) distributed at specific locations in the chamber. A differential mobility spectrometer was co-located with one of the CPCs for the measurement of particle size distributions (PSDs). The different modal groups present within the measured PSDs were determined through a log10-normal fitting program. Of the ventilation rates evaluated, the greatest relative improvement in particle concentration and clearance time occurred at the highest rate (12 air changes per hour, ACH). At the same time, indications of cross-contamination from regions with strong mixing conditions to regions where mixing was poor, were obtained showing that the latter could operate as particle traps where localised poor ventilation might occur. However, reducing the ventilation rate led to: i) an increase of leftover particles in the air of the chamber when the cleaning process had been completed, and more specifically to an increased ratio of ultrafine particles over fine ones, resulting in the potentially dangerous accumulation of contaminants with high exposure hazards, ii) a decrease in ventilation efficiency, which at low evacuation rates became independent of distance from the inlet diffuser, iii) slower clearance of resuspended particles, with the lowest efficiency at the moderate ventilation rate.

Improvement of the modeling of the low-temperature oxidation of n-butane: study of the primary reactions.

This paper revisits the primary reactions involved in the oxidation of n-butane from low to intermediate temperatures (550-800 K) including the negative temperature coefficient (NTC) zone. A model that was automatically generated is used as a starting point and a large number of thermochemical and kinetic data are then re-estimated. The kinetic data of the isomerization of alkylperoxy radicals giving (•)QOOH radicals and the subsequent decomposition to give cyclic ethers has been calculated at the CBS-QB3 level of theory. The newly obtained model allows a satisfactory prediction of experimental data recently obtained in a jet-stirred reactor and in rapid compression machines. A considerable improvement of the prediction of the selectivity of cyclic ethers is especially obtained compared to previous models. Linear and global sensitivity analyses have been performed to better understand which reactions are of influence in the NTC zone.

Global sensitivity analysis of chemical-kinetic reaction mechanisms: construction and deconstruction of the probability density function.

This paper investigates global sensitivity analysis as applied to reaction mechanisms. It uses the HDMR (high-dimensional model representation) expansion and the features of the sensitivity indices to explore the probability density function (pdf) of predicted target outputs that results from the uncertainties in the rate coefficients. We study the autoignition of H(2)/O(2) mixtures, where the pdf describes the uncertainty in ignition delay times due to the uncertainties in the rate coefficients. The global sensitivity analysis in conjunction with the HDMR expansion allows for the deconstruction of the pdf in several different ways. These deconstructions allow the features of the pdf to be understood in terms of the constitute reactions in much finer detail than the study of a variance decomposition alone.

Theoretical validation of chemical kinetic mechanisms: combustion of methanol.

A new technique is proposed that uses theoretical methods to systematically improve the performance of chemical kinetic mechanisms. Using a screening method, the chemical reaction steps that most strongly influence a given kinetic observable are identified. The associated rate coefficients are then improved by high-level quantum chemistry and transition-state-theory calculations, which leads to new values for the coefficients and smaller uncertainty ranges. This updating process is continued as new reactions emerge as the most important steps in the target observable. The screening process employed is a global sensitivity analysis that involves Monte Carlo sampling of the full N-dimensional uncertainty space of rate coefficients, where N is the number of reaction steps. The method is applied to the methanol combustion mechanism of Li et al. (Int. J. Chem. Kinet. 2007, 39, 109.). It was found that the CH(3)OH + HO(2) and CH(3)OH + O(2) reactions were the most important steps in setting the ignition delay time, and the rate coefficients for these reactions were updated. The ignition time is significantly changed for a broad range of high-concentration methanol/oxygen mixtures in the updated mechanism.

Suppression of nucleation mode particles by biomass burning in an urban environment: a case study.

Measurements of concentrations and size distributions of particles 4.7 to 160 nm were taken using an SMPS during the bonfire and firework celebrations on Bonfire Night in Leeds, UK, 2006. These celebrations provided an opportunity to study size distributions in a unique atmospheric pollution situation during and following a significant emission event due to open biomass burning. A log-normal fitting program was used to determine the characteristics of the modal groups present within hourly averaged size distributions. Results from the modal fitting showed that on bonfire night the smallest nucleation mode, which was present before and after the bonfire event and on comparison weekends, was not detected within the size distribution. In addition, there was a significant shift in the modal diameters of the remaining modes during the peak of the pollution event. Using the concept of a coagulation sink, the atmospheric lifetimes of smaller particles were significantly reduced during the pollution event, and thus were used to explain the disappearance of the smallest nucleation mode as well as changes in particle count mean diameters. The significance for particle mixing state is discussed.

Spatial dynamics of steady flames 1. Phase space structure and the dynamics of individual trajectories.

The spatial dynamics of steady, one-dimensional premixed H 2/O 2 flames are studied. The emphasis in this Article is the geometry of the phase space of the dynamical system describing the steady flames. It is shown that steady flames are described by trajectories on the stable manifolds of saddle fixed points. The saddle fixed points correspond to equilibrium points of time-dependent chemical-kinetic systems that are adiabatic and isobaric and whose constant enthalpy matches the asymptotic enthalpy of the flames. The dimensions of the stable manifolds match the dimensions of the chemical-kinetic systems under most conditions, although the dynamics on them are different. It is further shown that the stable manifolds have low-dimensional attractive submanifolds near the saddlepoint. An algorithm for generating trajectories over the spatial domain of these flames is proposed, and it is used to study individual trajectories and trajectory ensembles, whose collective behavior suggests that there are low-dimensional submanifolds away from the saddlepoint.

Spatial dynamics of steady flames 2. Low-dimensional manifolds and the role of transport processes.

The study of the spatial dynamics of steady one-dimensional H 2/O 2 flames is continued. Algorithms for generating low-dimensional manifolds for these systems are presented and used to find low-dimensional manifolds for the flames and the corresponding adiabatic, isobaric chemical-kinetic systems. It is demonstrated that these algorithms generate manifolds that are more accurate than the ILDM algorithm for two-dimensional manifolds of the flames. The manifolds are then employed to study the relationship between the manifolds of the flame and the manifolds of the chemical-kinetic system. It is shown that the one-dimensional manifolds of the flame match well with the composite manifolds of the chemical kinetics, but that for two-dimensional manifolds there are discrepancies between the flame manifolds and the chemical-kinetic manifolds.

Factors influencing particle number concentrations, size distributions and modal parameters at a roof-level and roadside site in Leicester, UK.

Measurements of urban particle number concentrations and size distributions in the range 5-1000 nm were taken at elevated (roof-level) and roadside sampling sites on Narborough Road in Leicester, UK, along with simultaneous measurements of traffic, NO(x), CO and 1,3-butadiene concentrations and meteorological parameters. A fitting program was used to determine the characteristics of up to five modal groups present in the particle size distributions. All particle modal concentrations peaked during the morning and evening rush hours. Additional events associated with the smallest mode, that were not observed to be connected to primary emissions, were also present suggesting that this mode consisted of newly formed secondary particles. These events included peaks in concentration which coincided with peaks in solar radiation, and lower concentrations of the larger modes. Investigation into the relationships between traffic flow and occupancy indicated three flow regimes; free-flow, unstable and congested. During free-flow conditions, positive linear relationships existed between traffic flow and particle modal number concentrations. However, during unstable and congested periods, this relationship was shown to break-down. Similar trends were observed for concentrations of the gas phase pollutants NO(x), CO and 1,3-butadiene. Strong linear relationships existed between NO(x), CO, 1,3-butadiene concentrations, nucleation and Aitken mode concentrations at both sampling locations, indicating a local traffic related emission source. At the roadside, both nucleation and Aitken mode are best represented by a decreasing exponential function with wind speed, whereas at the roof-level this relationship only occurred for Aitken mode particles. The differing relationships at the two sampling locations are most likely due to a combination of meteorological factors and distance from the local emission source.

Observations of urban airborne particle number concentrations during rush-hour conditions: analysis of the number based size distributions and modal parameters.

A summertime study of the number concentration and the size distribution of combustion derived nanometre sized particles (termed nanoparticles) from diesel and spark-ignition (SI) engine emissions were made under rush-hour and free-flow traffic conditions at an urban roadside location in Leeds, UK in July 2003. The measured total particle number concentrations (N(TOTAL)) were of the order 1.8 x 10(4) to 3.4 x 10(4) cm(-3), and tended to follow the diurnal traffic flow patterns. The N(TOTAL) was dominated by particles < or =100 nm in diameter which accounted for between 89-93% of the measured particle number. By use of a log-normal fitting procedure, the modal parameters of the number based particle size distribution of urban airborne particulates were derived from the roadside measurements. Four component modes were identified. Two nucleation modes were found, with a smaller, more minor, mode composed principally of sub-11 nm particles, believed to be derived from particles formed from the nucleation of gaseous species in the atmosphere. A second mode, much larger in terms of number, was composed of particles within the size range of 10-20 nm. This second mode was believed to be principally derived from the condensation of the unburned fuel and lube oil (the solvent organic fraction or SOF) as it cooled on leaving the engine exhaust. Third and fourth modes were noted within the size ranges of 28-65 nm and 100-160 nm, respectively. The third mode was believed to be representative of internally mixed Aitken mode particles composed of a soot/ash core with an adsorbed layer of readily volatilisable material. The fourth mode was believed to be composed of chemically aged, secondary particles. The larger nucleation and Aitken modes accounted for between 80-90% of the measured N(TOTAL), and the particles in these modes were believed to be derived from SI and diesel engine emissions. The overall size distribution, particularly in modes II-IV, was observed to be strongly related to the number of primary particle emissions, with larger count median diameters observed under conditions where low numbers of primary soot based particles were present.

Evaluation of models for the low temperature combustion of alkanes through interpretation of pressure-temperature ignition diagrams.

The purpose of this paper is to show the application of global uncertainty analysis to comprehensive and reduced kinetic models as a tool to identify important thermochemical and reaction rate parameters as determinants of the conditions leading to autoignition. Propane oxidation is taken as the test case. The simulation of experimental investigations of the cool flames and two-stage ignitions, via the pressure-temperature ignition diagram, show that existing kinetic models for the low temperature combustion of propane at sub-atmospheric pressures reflect a greater reactivity than seems to be appropriate. That is, the models lead to a prediction of two-stage ignition at pressures somewhat lower and with ignition delays shorter than is found experimentally. The inconsistency between experiment and numerical simulation seems not to be an inherent problem of the qualitative structure of the models, but may derive from uncertainties in the parameters within the mechanism. By use of "brute force", Morris-one-at-a-time and Monte-Carlo simulations, we show that uncertainties in only a small number of parameters, and falling well within the errors that may reasonably be assigned, can shift the response appropriately. Moreover, it appears that in the low temperature combustion regime, thermochemistry is at least as, if not more, important than the reaction rates, yet usually receives less attention within sensitivity studies. In the present case, the main factors controlling the temperature reached in the first stage of two-stage ignition and the time to ignition appear to be connected with the thermochemistry of three specific hydroperoxyalkyl radicals and their derivatives. Other factors, such as heat and mass transport are also addressed, and their effects are mitigated to some extent by evaluation of initial and revised models against experimental data for ignition delay obtained under microgravity. The results highlight more general issues that pertain to the numerical simulation of the combustion of higher hydrocarbons and contribute to the development of the protocol necessary for testing kinetic models before they are ready for use in a predictive capacity.

Genotoxicity of size-fractionated samples of urban particulate matter.

Urban particulate matter (UPM) includes particles of size smaller than 10 microm (PM10), which may impact on human respiratory and cardiovascular health. It has been reported previously that PM10 can induce DNA damage. We have collected size-fractionated PM10 at the roadside and measured the induction of DNA damage by different-sized UPM using the alkaline Comet assay and the plasmid strand-break assay. We found that foil disks were more suitable for collecting UPM than quartz fiber filters, as the UPM could be easily extracted from the foil disks and accurately weighed. Using the Comet assay, all size fractions induced DNA damage in A549 lung epithelial cells, with the finer fractions (D50% = 0.65 microm and lower) inducing the most damage. In the plasmid strand-break assay, in which DNA damage is induced by free-radical species generated in solution, the most damage was also induced by the finer fractions, although the finest fraction (D50% < 0.43 microm) did not induce as much damage as D50% = 0.65 and 0.43 microm. When an organic extract of a standard UPM sample was compared to the whole particles and the washed particles in the Comet assay, it was found that around 75% of the damage induced by the whole UPM could be induced by the organic extract. These results show that finer particulates have the greatest ability to induce DNA damage in lung epithelial cells and naked DNA, and that both organic and inorganic components of the UPM contribute to its genotoxic effects.