On the impact of the Bristol ChemLabS’ outreach programme on admissions to the School of Chemistry

Analysis of the average number of applicants received from schools that engaged in the Bristol ChemLabS Outreach program prior to a student‟s application with those that did not engage, shows a significant increase in applicants from engaged schools. The significance is weaker when just Post 16 students are considered but this is almost certainly due to a smaller sample size. When this analysis was inspected in terms of the distance of the school from the University of Bristol, there was an increase in the number of applicants from engaged schools irrespective of distance. However, a statistically significant increase was observed for schools within 50 miles of the University from an analysis of just Post 16 students. Students who applied to the department from an engaged school were more likely to accept an offer and also to make the department their firm acceptance. A slightly higher number of applications that were rejected came from engaged schools too. There are two possible reasons; first, the engagement may have encouraged more students who did not have the required entry qualifications. Second, during the period of analysis, the overall entry grades went up by one grade each year. Such a dramatic rise was probably the reason for the slightly elevated numbers

A five year record of high-frequency in situ measurements of non-methane hydrocarbons at Mace Head, Ireland

Continuous high-frequency in situ measurements of a range of non-methane hydrocarbons have been made at Mace Head since January 2005. Mace Head is a background Northern Hemispheric site situated on the eastern edge of the Atlantic. Five year measurements (2005–2009) of six C<sub>2</sub>–C<sub>5</sub> non-methane hydrocarbons have been separated into baseline Northern Hemispheric and European polluted air masses, among other sectors. Seasonal cycles in baseline Northern Hemispheric air masses and European polluted air masses arriving at Mace Head have been studied. Baseline air masses show a broad summer minima between June and September for shorter lived species, longer lived species show summer minima in July/August. All species displayed a winter maxima in February. European air masses showed baseline elevated mole fractions for all non-methane hydrocarbons. Largest elevations (of up to 360 ppt for ethane maxima) from baseline data were observed in winter maxima, with smaller elevations observed during the summer. Analysis of temporal trends using the Mann-Kendall test showed small (<6 % yr<sup>−1</sup>) but statistically significant decreases in the butanes and <i>i</i>-pentane between 2005 and 2009 in European air. No significant trends were found for any species in baseline air

Tracer concentration profiles measured in central London as part of the REPARTEE campaign

There have been relatively few tracer experiments carried out that have looked at vertical plume spread in urban areas. In this paper we present results from two tracer (cyclic perfluorocarbon) experiments carried out in 2006 and 2007 in central London centred on the BT Tower as part of the REPARTEE (Regent’s Park and Tower Environmental Experiment) campaign. The height of the tower gives a unique opportunity to study vertical dispersion profiles and transport times in central London. Vertical gradients are contrasted with the relevant Pasquill stability classes. Estimation of lateral advection and vertical mixing times are made and compared with previous measurements. Data are then compared with a simple operational dispersion model and contrasted with data taken in central London as part of the DAPPLE campaign. This correlates dosage with non-dimensionalised distance from source. Such analyses illustrate the feasibility of the use of these empirical correlations over these prescribed distances in central London

High-frequency urban measurements of molecular hydrogen and carbon monoxide in the United Kingdom

High-frequency measurements of atmospheric molecular hydrogen (H<sub>2</sub>) and carbon monoxide (CO) were made at an urban site in the United Kingdom (UK) from mid-December, 2008 until early March, 2009. Very few measurements of H<sub>2</sub> exist in the urban environment, particularly within the UK, but are an essential component in the assessment of anthropogenic emissions of H<sub>2</sub> and to a certain extent CO. These data provide detailed information on urban time-series, diurnal cycles as well as sources and sinks of both H<sub>2</sub> and CO at urban locations. High-frequency data were found to be strongly influenced by local meteorological conditions of wind speed and temperature. Diurnal cycles were found to follow transport frequency very closely due to the sites proximity to major carriageways, consequently a strong correlation was found between H<sub>2</sub> and CO mole fractions. Background subtracted mean and rush hour molar H<sub>2</sub>/CO emission ratios of 0.53±0.08 and 0.57±0.06 respectively, were calculated from linear fitting of data. The scatter plot of all H<sub>2</sub> and CO data displayed an unusual two population pattern, thought to be associated with a large industrial area 85 km to the west of the site. However, the definitive source of this two branch pattern could not be fully elucidated. H<sub>2</sub> emissions from transport in the UK were estimated to be 188±39 Gg H<sub>2</sub>/yr, with 8.1±2.3 Tg/yr of H<sub>2</sub> produced from vehicle emissions globally. H<sub>2</sub> and CO deposition velocities were calculated during stable night-time inversion events when a clear decay of both species was observed. CO was found to have a much higher deposition velocity than H<sub>2</sub>, 1.3±0.8×10<sup>−3</sup> and 2.2±1.5×10<sup>−4</sup> m s<sup>−1</sup> (1σ) respectively, going against the law of molecular diffusivity. The source of this unusual result was investigated, however no conclusive explanation was found for increased loss of CO over H<sub>2</sub> during stable night time inversion events

Predicting arene rate coefficients with respect to hydroxyl and other free radicals in the gas-phase: a simple and effective method using a single topological descriptor

International audienceThe reactivity of aromatic compounds is of great relevance to pure and applied chemical disciplines, yet existing methods for estimating gas-phase rate coefficients for their reactions with free radicals lack accuracy and universality. Here a novel approach is taken, whereby strong relationships between rate coefficients of aromatic hydrocarbons and a Randi?-type topological index are investigated, optimized and developed into a method which requires no specialist software or computing power. Measured gas-phase rate coefficients for the reaction of aromatic hydrocarbons with OH radicals were correlated with a calculated Randi?-type index, and optimized by including a term for side chain length. Although this method is exclusively for use with hydrocarbons, it is more diverse than any single existing methodology since it incorporates alkenylbenzenes into correlations, and can be extended towards other radical species such as O(3P) (and tentatively NO3, H and Cl). A comparison (with species common to both techniques) is made between the topological approach advocated here and a popular approach based on electrophilic subsituent constants, where it compares favourably. A modelling study was carried out to assess the impact of using estimated rate coefficients as opposed to measured data in an atmospheric model. The difference in model output was negligible for a range of NOx concentrations, which implies that this method has utility in complex chemical models. Strong relationships (e.g. for OH, R2=0.96) between seemingly diverse compounds including benzene, multisubstituted benzenes with saturated, unsaturated, aliphatic and cyclic substitutions and the nonbenzenoid aromatic, azulene suggests that the Randi?-type index presented here represents a new and effective way of describing aromatic reactivity, based on a quantitative structure-activity relationship (QSAR)

The CRI v2.2 reduced degradation scheme for isoprene

The reduced representation of isoprene degradation in the Common Representative Intermediates (CRI) mechanism has been systematically updated, using the Master Chemical Mechanism (MCM v3.3.1) as a reference benchmark, with the updated mechanism being released as CRI v2.2. The complete isoprene degradation mechanism in CRI v2.2 consists of 186 reactions of 56 closed shell and free radical species, this being an order of magnitude reduction in size compared with MCM v3.3.1. The chemistry initiated by reaction with OH radicals, NO3 radicals and ozone (O3) is treated. An overview of the updates is provided, within the context of reported kinetic and mechanistic information. The revisions mainly relate to the OH-initiated chemistry, which tends to dominate under atmospheric conditions, although these include updates to the chemistry of products that are also generated from the O3- and NO3-initiated oxidation. The revisions have impacts in a number of key areas, including recycling of HOx and NOx. The performance of the CRI v2.2 isoprene mechanism has been compared with those of the preceding version (CRI v2.1) and the reference MCM v3.3.1 over a range of relevant conditions, using a box model of the tropical forested boundary layer. In addition, tests are carried out to ensure that the performance of MCM v3.3.1 remains robust to more recently reported information. CRI v2.2 has also been implemented into the STOCHEM chemistry-transport model, with a customized close-variant of CRI v2.2 implemented into the EMEP MSC-W chemistry-transport model. The results of these studies are presented and used to illustrate the global-scale impacts of the mechanistic updates on HOx radical concentrations

Flipping the thinking on equality, diversity, and inclusion. why EDI is essential for the development and progression of the chemical sciences: A case study approach

All learners have a contribution to make to the development of the Chemical Sciences, be that in novel ways to teach, and their perspectives and contexts, but also in research, both in chemical education and the wider Chemical Sciences. Through four case studies, this paper explores interactions with diverse groups and how this has altered perspectives on both teaching and research. The case studies include work with visually impaired adults, a project bringing together First Peoples in Australia with academics to explore old ways (traditional science) and new ways (modern approaches), primary (elementary) school perspectives on teaching science, and a project in South Africa to connect university and township communities. Not only do these case studies demonstrate the immense value these diverse groups bring to our understanding about how to learn, but they also bring new perspectives on how to view and solve chemical problems

The effect of the novel HO_2 + NO → HNO_3 reaction channel at South Pole, Antarctica

It is well established that the reaction of HO_2 with NO plays a central role in atmospheric chemistry, by way of OH/HO_2 recycling and reduction of ozone depletion by HO_x cycles in the stratosphere and through ozone production in the troposphere. Utilizing a photochemical box model, we investigate the impact of the recently observed HNO_3 production channel (HO_2+NO → HNO_3) on NO_x (NO + NO_2), HO_x (OH + HO_2), HNO_3, and O_3 concentrations in the boundary layer at the South Pole, Antarctica. Our simulations exemplify decreases in peak O_3, NO, NO_2, and OH and an increase in HNO_3. Also, mean OH is in better agreement with observations, while worsening the agreement with O_3, HO_2, and HNO_3 concentrations observed at the South Pole. The reduced concentrations of NO_x are consistent with expected decreases in atmospheric NO_x lifetime as a result of increased sequestration of NO_x into HNO_3. Although we show that the inclusion of the novel HNO_3 production channel brings better agreement of OH with field measurements, the modelled ozone and HNO_3 are worsened, and the changes in NO_x lifetime imply that snowpack NO_x emissions and snowpack nitrate recycling must be re-evaluated