Near-Infrared Kinetic Spectroscopy of the HO_2 and C_2H_5O_2 Self-Reactions and Cross Reactions

The self-reactions and cross reactions of the peroxy radicals HO_2 and C_2H_5O_2 and HO_2 were monitored using simultaneous independent spectroscopic probes to observe each radical species. Wavelength modulation (WM) near-infrared (NIR) spectroscopy was used to detect HO_2, and UV absorption monitored HO_2 and C_2H_5O_2. The temperature dependences of these reactions were investigated over a range of interest to tropospheric chemistry, 221−296 K. The Arrhenius expression determined for the cross reaction, k_2(T) = (6.01^(+1.95)_(−1.47)) × 10^(−13) exp((638 ± 73)/T) cm^3 molecules^(−1) s^(−1) is in agreement with other work from the literature. The measurements of the HO_2 self-reaction agreed with previous work from this lab and were not further refined.(1) The C_2H_5O_2 self-reaction is complicated by secondary production of HO_2. This experiment performed the first direct measurement of the self-reaction rate constant, as well as the branching fraction to the radical channel, in part by measurement of the secondary HO_2. The Arrhenius expression for the self-reaction rate constant is k_3(T) = (1.29^(+0.34)_(−0.27)) × 10^(−13)exp((−23 ± 61)/T) cm^3 molecules^(−1) s^(−1), and the branching fraction value is α = 0.28 ± 0.06, independent of temperature. These values are in disagreement with previous measurements based on end product studies of the branching fraction. The results suggest that better characterization of the products from RO_2 self-reactions are required

Direct Detection of Products from the Pyrolysis of 2-Phenethyl Phenyl Ether

The pyrolysis of 2-phenethyl phenyl ether (PPE, C_6H_5C_2H_4OC_6H_5) in a hyperthermal nozzle (300-1350 °C) was studied to determine the importance of concerted and homolytic unimolecular decomposition pathways. Short residence times (<100 μs) and low concentrations in this reactor allowed the direct detection of the initial reaction products from thermolysis. Reactants, radicals, and most products were detected with photoionization (10.5 eV) time-of-flight mass spectrometry (PIMS). Detection of phenoxy radical, cyclopentadienyl radical, benzyl radical, and benzene suggest the formation of product by the homolytic scission of the C_6H_5C_2H_4-OC_6H_5 and C_6H_5CH_2-CH_2OC_6H_5 bonds. The detection of phenol and styrene suggests decomposition by a concerted reaction mechanism. Phenyl ethyl ether (PEE, C_6H_5OC_2H_5) pyrolysis was also studied using PIMS and using cryogenic matrix-isolated infrared spectroscopy (matrix-IR). The results for PEE also indicate the presence of both homolytic bond breaking and concerted decomposition reactions. Quantum mechanical calculations using CBS-QB3 were conducted, and the results were used with transition state theory (TST) to estimate the rate constants for the different reaction pathways. The results are consistent with the experimental measurements and suggest that the concerted retro-ene and Maccoll reactions are dominant at low temperatures (below 1000 °C), whereas the contribution of the C_6H_5C_2H_4-OC_6H_5 homolytic bond scission reaction increases at higher temperatures (above 1000 °C)

Development and Characterisation of a Gas System and its Associated Slow-Control System for an ATLAS Small-Strip Thin Gap Chamber Testing Facility

A quality assurance and performance qualification laboratory was built at McGill University for the Canadian-made small-strip Thin Gap Chamber (sTGC) muon detectors produced for the 2019-2020 ATLAS experiment muon spectrometer upgrade. The facility uses cosmic rays as a muon source to ionise the quenching gas mixture of pentane and carbon dioxide flowing through the sTGC detector. A gas system was developed and characterised for this purpose, with a simple and efficient gas condenser design utilizing a Peltier thermoelectric cooler (TEC). The gas system was tested to provide the desired 45 vol% pentane concentration. For continuous operations, a state-machine system was implemented with alerting and remote monitoring features to run all cosmic-ray data-acquisition associated slow-control systems, such as high/low voltage, gas system and environmental monitoring, in a safe and continuous mode, even in the absence of an operator.Comment: 23 pages, LaTeX, 14 figures, 4 tables, proof corrections for Journal of Instrumentation (JINST), including corrected Fig. 8b

Union économique et mobilité des facteurs; le cas de l'Union Économique et Monétaire Ouest Africain (UEMOA)

L'objet de ce papier est d'analyser les conséquences de la mise en place d'une Union économique entre les pays d'Afrique de l'Ouest (UEMOA), dans le cadre d'un modèle d'équilibre général calculable multi-pays avec mobilité des facteurs de production. On s'interroge sur les facteurs de convergence ou de divergence de développement, consécutifs à la réallocation des ressources et du commerce engendrés par la création de l'Union entre les pays membres qui, même s'ils ont des niveaux de revenus uniformément faibles, sont d'une configuration assez asymétrique. Tout d'abord, dans la mesure où l'Union économique signifie pour certains une forte ouverture internationale et pour d'autres un léger réarmement douanier, ses effets, de faible ampleur, sont contrastés. Par ailleurs, en dépit de l'asymétrie du choc, nos résultats sont conformes à ceux développés par Venables (1999): la Côte d'Ivoire qui possède le rapport des facteurs de production le moins éloigné du rapport mondial est le pays qui bénéficie le plus du processus d'intégration régionale. A l'inverse, le Burkina Faso voit sa situation se dégrader. La mobilité du travail et du capital industriel accentue le phénomène de divergence entre les pays de la zone. C'est ainsi que le Sénégal, et dans une moindre mesure le Togo, verraient à long terme leurs situations se dégrader par rapport au scénario de référence du fait de la fuite des capitaux industriels et donc leur écart de développement avec la Côte d'Ivoire croître. A contrario, la question migratoire, qui est parfois mise en exergue dans ce contexte, compte tenu des niveaux des flux et de l'ampleur somme toute modérée du choc macro-économique n'apparaît pas avec acuité. Enfin, on montre que la question de la transition fiscalo-douanière est centrale. En effet, selon le mode de financement des pertes fiscales choisi, l'impact des réformes douanières peut aller en sens opposé notamment sur la croissance des secteurs industriels dans des pays comme le Sénégal. Tant de problème du "creusement" du fossé entre la Côte d'Ivoire et ses partenaires régionaux et ses effets en terme de migration et de localisation du capital industriel dans la région, que le traitement du problème de la transition fiscalo-douanière doivent inciter la communauté internationale à envisager les politiques d'aide dans une stratégie régionale et non pas nationale comme cela l'est malheureusement encore.Intégration régionale, UEMOA, migration, FDI, MEGC

Toward Guidelines for Harvest Intensities and Regeneration Targets with Minimal Impact Upon Retained Genetic Diversity in Central Hardwood Tree Species

There is an urgent need for a coordinated and systematic approach to the in situ conservation of the genetic resources of commercially important forest tree species in the Central Hardwoods. Effective in situ management of genetic resources would benefit from clear guidelines for how many adult trees can be harvested with minimal impact on allelic diversity. We are constructing a computer model for this purpose, and present preliminary results based upon replicate harvests of a virtual forest stand consisting of 200 adult trees. Our model explores how much regeneration is needed so that there is no more than a 10 percent risk of retaining less than 90 percent of the original allelic diversity. In the absence of regeneration, up to 55 percent of the adult trees can be harvested without exceeding the 10 percent risk level. At higher harvest intensities, locally-derived regeneration is needed to replace the alleles removed from the adult population. When all 200 adult trees are harvested, the 10 percent risk level is not exceeded if there are at least 116 regenerants, provided that these are derived from pre-harvest random mating among the adults. In the presence of substantial pollen flow from a genetically differentiated outside pollen source (e.g., 10-20 percent pollen flow), the minimum amount of regeneration needed is reduced. This indicates that outside pollen can be more efficient, relative to pollen from within the stand, at replacing alleles lost from the adult population

Designing tools to predict and mitigate impacts on water quality following the Australian 2019/2020 wildfires: Insights from Sydney's largest water supply catchment

The 2019/20 Australian bushfires (or wildfires) burned the largest forested area in Australia's recorded history, with major socio‐economic and environmental consequences. Among the largest fires was the 280,000 ha Green Wattle Creek Fire which burned large forested areas of the Warragamba catchment. This protected catchment provides critical ecosystem services for Lake Burragorang, one of Australia's largest urban supply reservoirs delivering ~85 % of the water used in Greater Sydney. WaterNSW is the utility responsible for managing water quality in Lake Burragorang. Its postfire risk assessment, carried out in collaboration with researchers in Australia, the UK and USA, involved i) identifying pyrogenic contaminants in ash and soil; ii) quantifying ash loads and contaminant concentrations across the burned area; and iii) estimating the probability and quantity of soil, ash and associated contaminants entrainment for different rainfall scenarios. The work included refining the capabilities of the new WEPPcloud‐WATAR‐AU model (Water Erosion Prediction Project cloud‐Wildfire Ash Transport And Risk‐Australia) for predicting sediment, ash and contaminants transport, aided by outcomes from previous collaborative post‐fire research in the catchment. Approximately two weeks after the Green Wattle Creek Fire was contained, an extreme rainfall event (~276 mm in 72 h), caused extensive ash and sediment delivery into the reservoir. The risk assessment informed on‐ground monitoring and operational mitigation measures (deployment of debris‐catching booms and adjustment of the water supply system configuration), ensuring the continuity of safe water supply to Sydney. WEPPcloud‐WATAR‐AU outputs can prioritize recovery interventions for managing water quality risks by quantifying contaminants on the hillslopes, anticipating water contamination risk, and identifying areas with high susceptibility to ash and sediment transport. This collaborative interaction among scientists and water managers, aimed also at refining model capabilities and outputs to meet managers’ needs, exemplifies the successful outcomes that can be achieved at the interface of industry and science

Achieving sustainable construction within Private Finance Initiative (PFI) road projects in the UK

The construction industry is facing the challenge of increasing demands of its sustainability performance. The construction and maintenance of the built environment has substantial impact on the sustainability of the environment. Whist, public sector clients are increasingly asking for a sustainable approach in their specification and procurement decisions, sustainability is still seen as a novel concept within the construction industry in many parts of the world without a settled definition. The premise of this study is that the interaction between road projects realized by the private finance initiative and their delivery in the UK improve sustainability. The paper, based on case study research, explains the sustainability implementation in a PFI road project and demonstrates that the PFI mechanism facilitates sustainable implementation to a far greater extent than is achievable using traditional procurement methods