Simulation chamber studies of the atmospheric degradation of naphthalene, 1-nitronaphthalene and phthaldialdehyde

A detailed series of simulation chamber experiments has been performed on the atmospheric degradation pathways of the primary air pollutant naphthalene and two of its photooxidation products, phthaldialdehyde and 1-nitronaphthalene. The measured yields of secondary organic aerosol (SOA) arising from the photooxidation of naphthalene varied from 6-20%, depending on the concentrations of naphthalene and nitrogen oxides as well as relative humidity. A range of carbonyls, nitro-compounds, phenols and carboxylic acids were identified among the gas- and particle-phase products. On-line analysis of the chemical composition of naphthalene SOA was performed using aerosol time-of-flight mass spectrometry (ATOFMS) for the first time. The results indicate that enhanced formation of carboxylic acids may contribute to the observed increase in SOA yields at higher relative humidity. The photolysis of phthaldialdehyde and 1-nitronaphthalene was investigated using natural light at the European Photoreactor (EUPHORE) in Valencia, Spain. The photolysis rate coefficients were measured directly and used to confirm that photolysis is the major atmospheric loss process for these compounds. For phthaldialdehyde, the main gas-phase products were phthalide and phthalic anhydride. SOA yields in the range 2-11% were observed, with phthalic acid and dihydroxyphthalic acid identified among the particle phase products. The photolysis of 1-nitronaphthalene yielded nitric oxide and a naphthoxy radical which reacted to form several products. SOA yields in the range 57-71% were observed, with 1,4-naphthoquinone, 1-naphthol and 1,4-naphthalenediol identified in the particle phase. On-line analysis of the SOA generated in an indoor chamber using ATOFMS provided evidence for the formation of high-molecular-weight products. Further investigations revealed that these products are oxygenated polycyclic compounds most likely produced from the dimerization of naphthoxy radicals. These results of this work indicate that naphthalene is a potentially large source of SOA in urban areas and should be included in atmospheric models. The kinetic and mechanistic information could be combined with existing literature data to produce an overall degradation mechanism for naphthalene suitable for inclusion in photochemical models that are used to predict the effect of emissions on air quality.

Composition portfolio and commentaries

In an attempt to provide an analytical entry point into my compositional practice, I have identified eight themes which are significantly recurrent: reduction – the selection of a small number of elements; imperfection – a damaged or warped characteristic of sound; hierarchy – a concern with the roles of instruments with regard to their relative prominence; motion – apparently static sound masses consist of fine internal movement; listener perception – expectations for change influence the experience of affect; translation – the transitioning of electronic sounds to the acoustic realm, and vice versa; immersion – the creation of an accommodating soundscape; blurring – smearing and overlapping sounds or genres. Each of these eight factors is associated with relevant precedents in the history and theory of music that have been influential on my work. These include the minimalist compositions of Steve Reich and Arvo Pärt; the lo-fi aesthetic of Boards of Canada and My Bloody Valentine; concerns with political hierarchy in the work of Louis Andriessen; the variations of dynamics and microtonal shifts of Giacinto Scelsi; Leonard B. Meyer's account of expectation in music; cross-fertilisation of the acoustic and electronic in pieces by Gérard Grisey and Gyorgy Ligeti; the immersive technique of Brian Eno's ambient music; and the overlapping sounds of Aphex Twin. These eight factors are variously applicable to the eleven submitted pieces, which are individually analysed with reference to the most significant of the categories. Together they form a musical language that sustains the interaction of a variety of techniques, concepts and genres.

Chamber investigations of atmospheric mercury oxidation chemistry

Mercury is a potent neurotoxin even at low concentrations. The unoxidised metal has a high vapour pressure and can circulate through the atmosphere, but when oxidised can deposit and be accumulated through the food chain. This work aims to investigate the oxidation processes of atmospheric Hg0(g). The first part describes efforts to make a portable Hg sensor based on Cavity Enhanced Absorption Spectroscopy (CEAS). The detection limit achieved was 66 ngm−3 for a 10 second averaging time. The second part of this work describes experiments carried out in a temperature controlled atmospheric simulation chamber in the Desert Research Institute, Reno, Nevada, USA. The chamber was built around an existing Hg CRDS system that could measure Hg concentrations in the chamber of<100 ngm−3 at 1 Hz enabling reactions to be followed. The main oxidant studied was bromine, which was quantified with a LED based CEAS system across the chamber. Hg oxidation in the chamber was found to be mostly too slow for current models to explain. A seven reaction model was developed and tested to find which parameters were capable of explaining the deviation. The model was overdetermined and no unique solution could be found. The most likely possibility was that the first oxidation step Hg + Br →HgBr was slower than the preferred literature value by a factor of two. However, if the more uncertain data at low [Br2] was included then the only parameter that could explain the experiments was a fast, temperature independent dissociation of HgBr some hundreds of times faster than predicted thermolysis or photolysis rates. Overall this work concluded that to quantitatively understand the reaction of Hg with Br2, the intermediates HgBr and Br must be measured. This conclusion will help to guide the planning of future studies of atmospheric Hg chemistry.

Droplet etching of deep nanoholes for filling with self-aligned complex quantum structures

Strain-free epitaxial quantum dots (QDs) are fabricated by a combination of Al local droplet etching (LDE) of nanoholes in AlGaAs surfaces and subsequent hole filling with GaAs. The whole process is performed in a conventional molecular beam epitaxy (MBE) chamber. Autocorrelation measurements establish single-photon emission from LDE QDs with a very small correlation function g (2)(0)≃ 0.01 of the exciton emission. Here, we focus on the influence of the initial hole depth on the QD optical properties with the goal to create deep holes suited for filling with more complex nanostructures like quantum dot molecules (QDM). The depth of droplet etched nanoholes is controlled by the droplet material coverage and the process temperature, where a higher coverage or temperature yields deeper holes. The requirements of high quantum dot uniformity and narrow luminescence linewidth, which are often found in applications, set limits to the process temperature. At high temperatures, the hole depths become inhomogeneous and the linewidth rapidly increases beyond 640 °C. With the present process technique, we identify an upper limit of 40-nm hole depth if the linewidth has to remain below 100 μeV. Furthermore, we study the exciton fine-structure splitting which is increased from 4.6 μeV in 15-nm-deep to 7.9 μeV in 35-nm-deep holes. As an example for the functionalization of deep nanoholes, self-aligned vertically stacked GaAs QD pairs are fabricated by filling of holes with 35 nm depth. Exciton peaks from stacked dots show linewidths below 100 μeV which is close to that from single QDs.

Portfolio of compositions with commentaries 2012-2015

This writing forms part of a portfolio of works which gathers together notations and recordings made between 2012 and 2015. The writing divides into four chapters. The first chapter undertakes an examination of abstraction. From the proposition obtained therein, that it is possible to extend within abstraction beyond a correspondence between its terms and concrete manifestations, I ask in what way abstraction may be considered to function therefrom. The second chapter performs an analysis of radical music notations from the nineteenth, twentieth, and twenty-first centuries. The central analysis identifies what is essentially an evolution of what I call ''figuration'' throughout three non-chronological phases of Christian Wolff's notations. The chapter closes by questioning what form of understanding might yet be pursued in respect of this work given (a) its nature, and (b) the nature of our inquiry. The third chapter reflects on some of the philosophical problematics raised in the preceding chapters, at the same time as it prepares for those that follow in the final chapter. The final chapter is a record of the development of my thought appertaining to my compositional work. It sets out two case studies (prepared piano and postcard notations) before proceeding to a selected set of commentaries. Finally, the notion of the functioning of written and acoustical ''marks'' developed in the preceding commentaries is generalised as I develop an aesthetics of scriptural experience.