Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NOx and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively. Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.

Investigation into a best practice model for providing an integrated user experience with mobile cloud applications

Mobile Cloud Computing promises to overcome the physical limitations of mobile devices by executing demanding mobile applications on cloud infrastructure. In practice, implementing this paradigm is difficult; network disconnection often occurs, bandwidth may be limited, and a large power draw is required from the battery, resulting in a poor user experience. This thesis presents a mobile cloud middleware solution, Context Aware Mobile Cloud Services (CAMCS), which provides cloudbased services to mobile devices, in a disconnected fashion. An integrated user experience is delivered by designing for anticipated network disconnection, and low data transfer requirements. CAMCS achieves this by means of the Cloud Personal Assistant (CPA); each user of CAMCS is assigned their own CPA, which can complete user-assigned tasks, received as descriptions from the mobile device, by using existing cloud services. Service execution is personalised to the user's situation with contextual data, and task execution results are stored with the CPA until the user can connect with his/her mobile device to obtain the results. Requirements for an integrated user experience are outlined, along with the design and implementation of CAMCS. The operation of CAMCS and CPAs with cloud-based services is presented, specifically in terms of service description, discovery, and task execution. The use of contextual awareness to personalise service discovery and service consumption to the user's situation is also presented. Resource management by CAMCS is also studied, and compared with existing solutions. Additional application models that can be provided by CAMCS are also presented. Evaluation is performed with CAMCS deployed on the Amazon EC2 cloud. The resource usage of the CAMCS Client, running on Android-based mobile devices, is also evaluated. A user study with volunteers using CAMCS on their own mobile devices is also presented. Results show that CAMCS meets the requirements outlined for an integrated user experience.

Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.