Review of Informing the Inklings: George MacDonald and the Roots of Modern Fantasy

Review of Michael Partridge and Kirsten Jeffrey Johnson. Informing the Inklings: George MacDonald and the Roots of Modern Fantasy. (Hampden, CT: Winged Lion Press, 2018). 272 pages. ISBN 9781935688204

Development of an apparatus for time resolved measurement of OH and HO2, with application to atmospherically relevant reactions.

The primary focus of this work has been to develop and characterize an instrument for the time resolved (millisecond timescale) measurement of OH and HO2, to monitor reactions occurring under high pressures (500 – 4000 mbar), and over a wide range of temperatures (290 – 700 K). This instrument was then used in conjunction with PTR-TOF-MS and conventional slow-flow reactors to study the OH initiated oxidation of a range of nitrogen containing compounds. Chapter 3 describes the development of this system and its characterization. Of particular importance to later work, it was noted that measuring the temperature of a flowing gas with a thermocouple could be highly inaccurate. Following this observation, chemical thermometers (e.g. the reaction of OH and methane) were instead used to assign the temperature at which reactions were occurring in the high-pressure system (and this was later extended to conventional slow-flow systems). HO2 detection was carried out indirectly via titration with NO to form OH, which was then detected by LIF. Efficient and selective titration of HO2 could only be achieved beyond the breakdown of the jet in the low-pressure detection cell, and as such, time resolution of the HO2 signal was reduced compared with the OH measurements. However, HO2 yield could be achieved with high accuracy and precision. This was validated for the reaction of OH with methanol under high (6 ×1018 cm-3) and low oxygen (<1×1016 cm-3) conditions; where the measured yields of 87 ± 5 % at low oxygen, and 99 ± 2 % at high oxygen were in excellent agreement with the expected yields of 85 ± 8 % and 100 % from McCaulley et al..(1) In chapter 4, this apparatus was applied to study the OH initiated oxidation of n-butanol (a potential ‘drop in’ biofuel); where, the measurement of OH recycling, and HO2 yields allowed for the assignment of α and β branching fractions. The measured branching ratios were β = 0.24 ± 0.04 (616 – 640 K), and α= (0.57 ± 0.06) at 293 K, and (0.54 ± 0.04) at 616 K). Understanding the ratio of the α and β branching fractions for OH abstraction from n-butanol is important in modelling its ignition delay time, with α leading to the formation of HO2 a chain inhibiting reaction. Chapter 5 and 6 describe the study of the OH initiated oxidation of methyl formamide (MF), dimethyl formamide (DMF), tertiary butyl amine (tBA), and methyl propane diamine (diamine). In chapter 5, the temperature dependence of the OH oxidation of dimethyl formamide was studied, and particular emphasis was placed on the source of OH recycling that becomes prevalent above 450 K. The overall temperature dependence of OH and DMF was assigned as "k" _"OH+DMF" "=(1.317± 0.117)×" 〖"10" 〗^"-11" 〖"(" "T" /"298" ")" 〗^"-0.5" "e" ^"37.16/RT" , with an ambient temperature value of k298 K= (1.30 ± 0.12) × 10-11 cm3 molecule-1 s-1. High level computational calculations (CCSD(T)/CBS//mp2/6-311++g(3df,3pd)) were carried out to generate potential energy surfaces for the abstraction reactions and the subsequent R + O2 surfaces. The results of both the experimental and computational work carried out, indicated that the majority abstraction over all temperatures was from the aldehydic position. This is of atmospheric significance as it is a route to the formation of a nitrogen centred radical, which can lead to the formation of dimethyl nitramine and dimethyl nitrosamine. Nitramines and nitrosamines are potent carcinogenic compounds. Chapter 7 used the reaction of OH and isoprene to illustrate potential differences in the chemistry observed when the reaction was carried under different experimental conditions, where the reactions were monitored using PTR-TOF-MS. The well-defined ambient temperature rate coefficient of OH and isoprene allowed it to be used as a reference compound for a relative rate study of OH and 1,3,5- tri methyl benzene (TMB) which was carried out in EUPHORE and HIRAC giving kOH+TMB = (5.77 ± 0.05) × 10-11 cm3 molecule-1 s-1. From reactions carried out in EUPHORE, an ambient pressure quartz reactor, and the high pressure system (at 1000 mbar) the combined yield of methacrolein and methyl vinyl ketone was shown to be > 70 % in good agreement with that observed by Sprengnether et al. (72 ± 7 %).(2) In addition, from the reactions carried out in HIRAC, an ambient pressure quartz reactor, and the high pressure system the yield of m/z 83 was assigned as 3 – 7 % at room temperature and was identified as the product of the abstraction, not of 3-MF (3-methyl furan). The homogenous pathway to 3-MF is not well known, and at room temperature when the reaction were carried out in the high-pressure reactor, and the quartz reactor secondary OH chemistry and heterogeneous routes were minimized. 1. MCCAULLEY, J., N. KELLY, M. GOLDE and F. KAUFMAN. Kinetic studies of the reactions of F and OH with CH3OH, The Journal of Physical Chemistry, 1989, 93(3), pp.1014-1018. 2. SPRENGNETHER, M., K.L. DEMERJIAN, N.M. DONAHUE and J.G. ANDERSON. Product analysis of the OH oxidation of isoprene and 1,3-butadiene in the presence of NO. Journal of Geophysical Research: Atmospheres, 2002, 107(D15), pp.ACH 8-1-ACH 8-13

Confirmatory factor analysis of a two scale model of the Health of the Nation Outcome Scales (HoNOS) across diagnostic categories

The study examines the fit of a two factor model of the Health of the Nation Outcome scales fo r a large sample of patients referred to mental health services in England . The fit of the model for different diagnostic groups delineated by the Engli sh mental health cluster system is investigated. O verall the fit of the model is excellent at the super cluster level of psychotic disorders, organic disorders and good for non - psychotic disorders. It is, however, not as good at the cluster level

Thermal comfort and perceptions of the ecosystem services and disservices of urban trees in florence

Modern urban lifestyles have most likely generated a loss of awareness of the bio-cultural benefits derived from the presence of trees and forests in cities. The present study aimed at understanding the level of awareness and the ability to express significant relationships, both positive and negative, on ecosystem services and disservices by the citizens of a Mediterranean city where thermal comfort during the summer period can be particularly problematic. A questionnaire consisting of multiple-choice and open-ended questions was disseminated to citizens of Florence, Italy. The open questions allowed respondents space to describe what they perceive are the benefits and disbenefits of urban trees. Meanwhile, geospatial and climate data were processed in order to check the vegetation and microclimate conditions of the city areas where the 592 respondents live. The vast majority of respondents felt Florence is unbearably hot in summer with 93% agreeing the city needs more trees, and shaded places were perceived as the most important feature of urban green space. The results reveal many positive and negative associations to different species of trees and bring out a rich mosaic of perceptions towards urban green spaces and the features they contain. People are generally aware of a wide range of the benefits trees provide to communities and a good knowledge of the microclimate modification properties was revealed. Many of the popular public tree genera in the city, such as Tilia, Platanus and Pinus were favoured by residents however there was some overlap with trees that provoke negative experiences, and this information can be useful to city planners aiming to maximise ecosystem services and minimise ecosystem disservices

A new instrument for time-resolved measurement of HO2 radicals

OH and HO2 radicals are closely coupled in the atmospheric oxidation and combustion of volatile organic compounds (VOCs). Simultaneous measurement of HO2 yields and OH kinetics can provide the ability to assign site-specific rate coefficients that are important for understanding the oxidation mechanisms of VOCs. By coupling a fluorescence assay by gaseous expansion (FAGE) laser-induced fluorescence (LIF) detection system for OH and HO2 with a high-pressure laser flash photolysis system, it is possible to accurately measure OH pseudo-1st-order loss processes up to ∼100 000 s−1 and to determine HO2 yields via time-resolved measurements. This time resolution allows discrimination between primary HO2 from the target reaction and secondary production from side reactions. The apparatus was characterized by measuring yields from the reactions of OH with H2O2 (1:1 link between OH and HO2), with C2H4∕O2 (where secondary chemistry can generate HO2), with C2H6∕O2 (where there should be zero HO2 yield), and with CH3OH∕O2 (where there is a well-defined HO2 yield). As an application of the new instrument, the reaction of OH with n-butanol has been studied at 293 and 616 K. The bimolecular rate coefficient at 293 K, (9.24±0.21)×10−12 cm3 molec.−1 s−1, is in good agreement with recent literature, verifying that this instrument can measure accurate OH kinetics. At 616 K the regeneration of OH in the absence of O2, from the decomposition of the β-hydroxy radical, was observed, which allowed the determination of the fraction of OH reacting at the β site (0.23±0.04). Direct observation of the HO2 product in the presence of oxygen has allowed the assignment of the α-branching fractions (0.57±0.06) at 293 K and (0.54±0.04) at 616 K, again in good agreement with recent literature; branching ratios are key to modelling the ignition delay times of this potential “drop-in” biofuel