Radiative efficiencies and global warming potentials using theoretically determined absorption cross-sections for several hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs)

Integrated infrared cross-sections and wavenumber positions for the vibrational modes of a range of hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs) have been calculated. Spectra were determined using a density functional method with an empirically derived correction for the wavenumbers of band positions. Radiative efficiencies (REs) were determined using the Pinnock et al. method and were used with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). For the HFEs and the majority of the molecules in the HG series HFPEs, theoretically determined absorption cross-sections and REs lie within ca. 10% of those determined using measured spectra. For the larger molecules in the HG series and the HG′ series of HFPEs, agreement is less good, with theoretical values for the integrated cross-sections being up to 35% higher than the experimental values; REs are up to 45% higher. Our method gives better results than previous theoretical approaches, because of the level of theory chosen and, for REs, because an empirical wavenumber correction derived for perfluorocarbons is effective in predicting the positions of C–F stretching frequencies at around 1250 cm−1 for the molecules considered here.

A study of the atmospherically relevant reaction between molecular chlorine and dimethylsulfide (DMS): establishing the reaction intermediate and measurement of absolute photoionization cross-sections

In a study using UV photoelectron spectroscopy (PES) of the atmospherically relevant reaction CH3SCH3 + Cl2 → CH3SCH2Cl + HCl bands associated with a reaction intermediate have been observed. These have been assigned to ionization of the covalently bound molecule (CH3)2SCl2 on the basis of the intensity of the observed bands as a function of reaction time, molecular orbital calculations of vertical ionization energies and evidence from infrared spectroscopy. A method has also been developed, with the flow-tube/PE spectrometer combination used, to measure photoionization cross-sections of the reagents and products at the photon energy utilized and this has allowed the photoionization cross-section of the intermediate to be estimated. This work augments an earlier study in which the rate constant of the reaction between CH3SCH3 (DMS) and Cl2 has been measured at room temperature.

Globalisation and the evolution of international retailing: a comment on Alexander's 'British overseas retailing, 1900-1960'

Nicholas Alexander's (2011. British overseas retailing, 1900–60: International firm characteristics, market selections and entry modes. Business History, 53, 530–556) survey of British overseas retailers from 1900 to 1960 provides pathbreaking new evidence of international retailing activity during the first globalisation boom. The article surveys this and other recent evidence, and confirms that international retailing was far more significant up to 1929 than previously thought. This activity was overwhelmingly undertaken by non-retailers, however, and hence by multinationals whose advantages in retailing were fundamentally unsustainable over the long run. Even the department store format, the principal retail innovation of the period, was not internationalised primarily by multinationals. Rather it was diffused via indigenous entrepreneurs, driven by a rapidly growing global demand for western style fashion and dress.

Comment on “A modified leapfrog scheme for shallow water equations” by Wen-Yih Sun and Oliver M.T. Sun

A recent paper published in this journal considers the numerical integration of the shallow-water equations using the leapfrog time-stepping scheme [Sun Wen-Yih, Sun Oliver MT. A modified leapfrog scheme for shallow water equations. Comput Fluids 2011;52:69–72]. The authors of that paper propose using the time-averaged height in the numerical calculation of the pressure-gradient force, instead of the instantaneous height at the middle time step. The authors show that this modification doubles the maximum Courant number (and hence the maximum time step) at which the integrations are stable, doubling the computational efficiency. Unfortunately, the pressure-averaging technique proposed by the authors is not original. It was devised and published by Shuman [5] and has been widely used in the atmosphere and ocean modelling community for over 40 years.

Building simulation

This chapter aims to provide an overview of building simulation in a theoretical and practical context. The following sections demonstrate the importance of simulation programs at a time when society is shifting towards a low carbon future and the practice of sustainable design becomes mandatory. The initial sections acquaint the reader with basic terminology and comment on the capabilities and categories of simulation tools before discussing the historical development of programs. The main body of the chapter considers the primary benefits and users of simulation programs, looks at the role of simulation in the construction process and examines the validity and interpretation of simulation results. The latter half of the chapter looks at program selection and discusses software capability, product characteristics, input data and output formats. The inclusion of a case study demonstrates the simulation procedure and key concepts. Finally, the chapter closes with a sight into the future, commenting on the development of simulation capability, user interfaces and how simulation will continue to empower building professionals as society faces new challenges in a rapidly changing landscape.

Comment on ``Conditional Exceedance Probabilities''

In a recent paper, Mason et al. propose a reliability test of ensemble forecasts for a continuous, scalar verification. As noted in the paper, the test relies on a very specific interpretation of ensembles, namely, that the ensemble members represent quantiles of some underlying distribution. This quantile interpretation is not the only interpretation of ensembles, another popular one being the Monte Carlo interpretation. Mason et al. suggest estimating the quantiles in this situation; however, this approach is fundamentally flawed. Errors in the quantile estimates are not independent of the exceedance events, and consequently the conditional exceedance probabilities (CEP) curves are not constant, which is a fundamental assumption of the test. The test would reject reliable forecasts with probability much higher than the test size.

Comment on “Multiyear prediction of monthly mean Atlantic meridional overturning circulation at 26.5°N”

Matei et al. (Reports, 6 January 2012, p. 76) claim to show skillful multiyear predictions of the Atlantic Meridional Overturning Circulation (AMOC). However, these claims are not justified, primarily because the predictions of AMOC transport do not outperform simple reference forecasts based on climatological annual cycles. Accordingly, there is no justification for the “confident” prediction of a stable AMOC through 2014.

Measuring research benefits in an imperfect market: second comment

This note generalizes a finding about the necessary and sufficient conditions for research to generate greater benefits in the presence of distortions and highlights a significant source of bias in conventional cost-benefit calculations

Comment on "Tropospheric temperature response to stratospheric ozone recovery in the 21st century" by Hu et al. (2011)

Abstract. In a recent paper Hu et al. (2011) suggest that the recovery of stratospheric ozone during the first half of this century will significantly enhance free tropospheric and surface warming caused by the anthropogenic increase of greenhouse gases, with the effects being most pronounced in Northern Hemisphere middle and high latitudes. These surprising results are based on a multi-model analysis of CMIP3 model simulations with and without prescribed stratospheric ozone recovery. Hu et al. suggest that in order to properly quantify the tropospheric and surface temperature response to stratospheric ozone recovery, it is necessary to run coupled atmosphere-ocean climate models with stratospheric ozone chemistry. The results of such an experiment are presented here, using a state-of-the-art chemistry-climate model coupled to a three-dimensional ocean model. In contrast to Hu et al., we find a much smaller Northern Hemisphere tropospheric temperature response to ozone recovery, which is of opposite sign. We suggest that their result is an artifact of the incomplete removal of the large effect of greenhouse gas warming between the two different sets of models.