Biogeochemical properties of sinking particles intercepted at three depths on the NW Atlantic margin

Three conical sediment were deployed at three depths 968 m (top trap), 1976 m (middletrap), and 2938 m (50mabove the bottom, bottom trap) - from June 27, 2004 to April 27, 2005 on the NW Atlantic margin at a water depth of 2988 m. The sediment trap carousels were programmed to open each collection cup for 23.4 days for the top trap and 14.5 days for the other two traps, resulting in total 13 samples from the top trap and 21 samples each from the middle and bottom traps. The samples were analyzed for the biogeochemical properties with various methods. Frequent occurrences of higher fluxes in deep relative to shallower sediment traps and low delta 14C values of sinking POC together provide strong evidence for significant lateral transport of aged organic matter over the margin. Comparison of biogeochemical properties such as aluminum concentration and flux, and iron concentration between samples intercepted at different depths shows that particles collected by the deepest trap had more complex sources than the shallower ones. These data also suggest that at least two modes of lateral transport exist over the New England margin. Based on radio carbon mass balance, about 30% (± 10%) of sinking POC in all sediment traps is estimated to be derived from lateral transport of re-suspended sediment. A strong correlation between delta 14C values and aluminum concentrations suggests that the aged organic matter is associated with lithogenic particles.

Diesel bus emissions of submicrometer particles measured in a tunnel study

The emission factors of a bus fleet consisting of approximately three hundreds diesel powered buses were measured in a tunnel study under well controlled conditions during a two-day monitoring campaign in Brisbane. The number concentration of particles in the size range 0.017-0.7 m was monitored simultaneously by two Scanning Mobility Particle Sizers located at the tunnel’s entrance and exit. The mean value of the number emission factors was found to be (2.44±1.41)×1014 particles km-1. The results are in good agreement with the emission factors determined from steady-state dynamometer testing of 12 buses from the same Brisbane City bus fleet, thus indicating that when carefully designed, both approaches, the dynamometer and on-road studies, can provide comparable results, applicable for the assessment of the effect of traffic emissions on airborne particle pollution.

Indoor exposure to submicrometer particles and PM2.5 in residential houses in Brisbane, Australia

As part of a large study investigating indoor air in residential houses in Brisbane, Australia, the purpose of this work was to quantify indoor exposure to submicrometer particles and PM2.5 for the inhabitants of 14 houses. Particle concentrations were measured simultaneously for more than 48 hours in the kitchens of all the houses by using a condensation particle counter (CPC) and a photometer (DustTrak). The occupants of the houses were asked to fill in a diary, noting the time and duration of any activity occurring throughout the house during measurement, as well as their presence or absence from home. From the time series concentration data and the information about indoor activities, exposure to the inhabitants of the houses was calculated for the entire time they spent at home as well as during indoor activities resulting in particle generation. The results show that the highest median concentration level occurred during cooking periods for both particle number concentration (47.5´103 particles cm-3) and PM2.5 concentration (13.4 mg m-3). The highest residential exposure period was the sleeping period for both particle number exposure (31%) and PM2.5 exposure (45.6%). The percentage of the average residential particle exposure level in total 24h particle exposure level was approximating 70% for both particle number and PM2.5 exposure.

Relationship between indoor/outdoor concentrations of particles : a critical review

The relationship between indoor and outdoor concentration levels of particles in the absence and in the presence of indoor sources has been attracting an increasing level of attention. Understanding of the relationship and the mechanisms driving it, as well as the ability to quantify it, are of importance for assessment of source contribution, assessment of human exposure and for control and management of particles. It became particularly important to address this topic when evidence came from epidemiological studies on the close association between outdoor concentration levels of particles and health effects, yet with many studies showing that indoor concentrations could be significantly higher than those outdoors. This paper presents a summary of an extensive literature review on this topic conducted with an aim to identify general trends in relation to the I/O relationship emerging from studies conducted worldwide. The review considered separately a larger body of papers published on PM10, PM2.5, as well as the smaller database on particle number and number or volume size distribution. A specific focus of this paper is on naturally ventilated houses. The conclusion from the review is that despite the multiplicity of factors that play role in affecting the relationship, there are clear trends emerging in relation to the I/O relationship for particle mass concentration, enabling more general predictions to be made about the relationship. However, more research is still needed on particle number concentration and size distribution.

On the efficiency of impingers with fritted nozzle tip for collection of ultrafine particles

The aim of this study was to determine the collection efficiency of ultrafine particles into an impinger fitted with a fritted nozzle tip as a means to increase contact surface area between the aerosol and the liquid. The influence of liquid sampling volume, frit porosity and the nature of the sampling liquid was explored and it was shown that all impact on the collection efficiency of particles smaller than 220 nm. Obtained values for overall collection efficiency were substantially higher (~30–95%) than have been previously reported, mainly due to the high deposition of particles in the fritted nozzle tip, especially in case of finer porosity frits and smaller particles. Values for the capture efficiency of the solvent alone ranged from 20 to 45%, depending on the type and the volume of solvent. Additionally, our results show that airstream dispersion into bubbles improves particle trapping by the liquid and that there is a difference in collection efficiencies based on the nature and volume of the solvent used.

Ultrafine particles in indoor air of a school : possible role of secondary organic aerosols

The aim of this work was to investigate ultrafine particles (< 0.1 μm) in primary school classrooms, in relation to the classrooms activities. The investigations were conducted in three classrooms during two measuring campaigns, which together encompassed a period of 60 days. Initial investigations showed that under the normal operating conditions of the school there were many occasions in all three classrooms where indoor particle concentrations increased significantly compared to outdoor levels. By far the highest increases in the classroom resulted from art activities (painting, gluing and drawing), at times reaching over 1.4 x 105 particle cm-3. The indoor particle concentrations exceeded outdoor concentrations by approximately one order of magnitude, with a count median diameter ranging from 20-50 nm. Significant increases also occurred during cleaning activities, when detergents were used. GC-MS analysis conducted on 4 samples randomly selected from about 30 different paints and glues, as well as the detergent used in the school, showed that d-limonene was one of the main organic compounds of the detergent, however, it was not detected in the samples of the paints and the glue. Controlled experiments showed that this monoterpene, emitted from the detergent, reacted with O3 (at outdoor ambient concentrations ranging from 0.06-0.08ppm) and formed secondary organic aerosols. Further investigations to identify other liquids which may be potential sources of the precursors of secondary organic aerosols, were outside the scope of this project, however, it is expected that the problem identified by this study could be more widely spread, since most primary schools use liquid materials for art classes, and all schools use detergents for cleaning. Further studies are therefore recommended to better understand this phenomenon and also to minimize school children exposure to ultrafine particles from these indoor sources.

Intelligent prognostics of machinery health utilising suspended condition monitoring data

The ability to forecast machinery failure is vital to reducing maintenance costs, operation downtime and safety hazards. Recent advances in condition monitoring technologies have given rise to a number of prognostic models for forecasting machinery health based on condition data. Although these models have aided the advancement of the discipline, they have made only a limited contribution to developing an effective machinery health prognostic system. The literature review indicates that there is not yet a prognostic model that directly models and fully utilises suspended condition histories (which are very common in practice since organisations rarely allow their assets to run to failure); that effectively integrates population characteristics into prognostics for longer-range prediction in a probabilistic sense; which deduces the non-linear relationship between measured condition data and actual asset health; and which involves minimal assumptions and requirements. This work presents a novel approach to addressing the above-mentioned challenges. The proposed model consists of a feed-forward neural network, the training targets of which are asset survival probabilities estimated using a variation of the Kaplan-Meier estimator and a degradation-based failure probability density estimator. The adapted Kaplan-Meier estimator is able to model the actual survival status of individual failed units and estimate the survival probability of individual suspended units. The degradation-based failure probability density estimator, on the other hand, extracts population characteristics and computes conditional reliability from available condition histories instead of from reliability data. The estimated survival probability and the relevant condition histories are respectively presented as “training target” and “training input” to the neural network. The trained network is capable of estimating the future survival curve of a unit when a series of condition indices are inputted. Although the concept proposed may be applied to the prognosis of various machine components, rolling element bearings were chosen as the research object because rolling element bearing failure is one of the foremost causes of machinery breakdowns. Computer simulated and industry case study data were used to compare the prognostic performance of the proposed model and four control models, namely: two feed-forward neural networks with the same training function and structure as the proposed model, but neglected suspended histories; a time series prediction recurrent neural network; and a traditional Weibull distribution model. The results support the assertion that the proposed model performs better than the other four models and that it produces adaptive prediction outputs with useful representation of survival probabilities. This work presents a compelling concept for non-parametric data-driven prognosis, and for utilising available asset condition information more fully and accurately. It demonstrates that machinery health can indeed be forecasted. The proposed prognostic technique, together with ongoing advances in sensors and data-fusion techniques, and increasingly comprehensive databases of asset condition data, holds the promise for increased asset availability, maintenance cost effectiveness, operational safety and – ultimately – organisation competitiveness.

Dynamics of transformation and fragmentation of composite liquid nano-particles

Recent research on particle size distributions and particle concentrations near a busy road cannot be explained by the conventional mechanisms for particle evolution of combustion aerosols. Specifically they appear to be inadequate to explain the experimental observations of particle transformation and the evolution of the total number concentration. This resulted in the development of a new mechanism based on their thermal fragmentation, for the evolution of combustion aerosol nano-particles. A complex and comprehensive pattern of evolution of combustion aerosols, involving particle fragmentation, was then proposed and justified. In that model it was suggested that thermal fragmentation occurs in aggregates of primary particles each of which contains a solid graphite/carbon core surrounded by volatile molecules bonded to the core by strong covalent bonds. Due to the presence of strong covalent bonds between the core and the volatile (frill) molecules, such primary composite particles can be regarded as solid, despite the presence of significant (possibly, dominant) volatile component. Fragmentation occurs when weak van der Waals forces between such primary particles are overcome by their thermal (Brownian) motion. In this work, the accepted concept of thermal fragmentation is advanced to determine whether fragmentation is likely in liquid composite nano-particles. It has been demonstrated that at least at some stages of evolution, combustion aerosols contain a large number of composite liquid particles containing presumably several components such as water, oil, volatile compounds, and minerals. It is possible that such composite liquid particles may also experience thermal fragmentation and thus contribute to, for example, the evolution of the total number concentration as a function of distance from the source. Therefore, the aim of this project is to examine theoretically the possibility of thermal fragmentation of composite liquid nano-particles consisting of immiscible liquid v components. The specific focus is on ternary systems which include two immiscible liquid droplets surrounded by another medium (e.g., air). The analysis shows that three different structures are possible, the complete encapsulation of one liquid by the other, partial encapsulation of the two liquids in a composite particle, and the two droplets separated from each other. The probability of thermal fragmentation of two coagulated liquid droplets is discussed and examined for different volumes of the immiscible fluids in a composite liquid particle and their surface and interfacial tensions through the determination of the Gibbs free energy difference between the coagulated and fragmented states, and comparison of this energy difference with the typical thermal energy kT. The analysis reveals that fragmentation was found to be much more likely for a partially encapsulated particle than a completely encapsulated particle. In particular, it was found that thermal fragmentation was much more likely when the volume ratio of the two liquid droplets that constitute the composite particle are very different. Conversely, when the two liquid droplets are of similar volumes, the probability of thermal fragmentation is small. It is also demonstrated that the Gibbs free energy difference between the coagulated and fragmented states is not the only important factor determining the probability of thermal fragmentation of composite liquid particles. The second essential factor is the actual structure of the composite particle. It is shown that the probability of thermal fragmentation is also strongly dependent on the distance that each of the liquid droplets should travel to reach the fragmented state. In particular, if this distance is larger than the mean free path for the considered droplets in the air, the probability of thermal fragmentation should be negligible. In particular, it follows form here that fragmentation of the composite particle in the state with complete encapsulation is highly unlikely because of the larger distance that the two droplets must travel in order to separate. The analysis of composite liquid particles with the interfacial parameters that are expected in combustion aerosols demonstrates that thermal fragmentation of these vi particles may occur, and this mechanism may play a role in the evolution of combustion aerosols. Conditions for thermal fragmentation to play a significant role (for aerosol particles other than those from motor vehicle exhaust) are determined and examined theoretically. Conditions for spontaneous transformation between the states of composite particles with complete and partial encapsulation are also examined, demonstrating the possibility of such transformation in combustion aerosols. Indeed it was shown that for some typical components found in aerosols that transformation could take place on time scales less than 20 s. The analysis showed that factors that influenced surface and interfacial tension played an important role in this transformation process. It is suggested that such transformation may, for example, result in a delayed evaporation of composite particles with significant water component, leading to observable effects in evolution of combustion aerosols (including possible local humidity maximums near a source, such as a busy road). The obtained results will be important for further development and understanding of aerosol physics and technologies, including combustion aerosols and their evolution near a source.

Theoretical investigation of mechanisms of formation and interaction of nanoparticles

In this thesis an investigation into theoretical models for formation and interaction of nanoparticles is presented. The work presented includes a literature review of current models followed by a series of five chapters of original research. This thesis has been submitted in partial fulfilment of the requirements for the degree of doctor of philosophy by publication and therefore each of the five chapters consist of a peer-reviewed journal article. The thesis is then concluded with a discussion of what has been achieved during the PhD candidature, the potential applications for this research and ways in which the research could be extended in the future. In this thesis we explore stochastic models pertaining to the interaction and evolution mechanisms of nanoparticles. In particular, we explore in depth the stochastic evaporation of molecules due to thermal activation and its ultimate effect on nanoparticles sizes and concentrations. Secondly, we analyse the thermal vibrations of nanoparticles suspended in a fluid and subject to standing oscillating drag forces (as would occur in a standing sound wave) and finally on lattice surfaces in the presence of high heat gradients. We have described in this thesis a number of new models for the description of multicompartment networks joined by a multiple, stochastically evaporating, links. The primary motivation for this work is in the description of thermal fragmentation in which multiple molecules holding parts of a carbonaceous nanoparticle may evaporate. Ultimately, these models predict the rate at which the network or aggregate fragments into smaller networks/aggregates and with what aggregate size distribution. The models are highly analytic and describe the fragmentation of a link holding multiple bonds using Markov processes that best describe different physical situations and these processes have been analysed using a number of mathematical methods. The fragmentation of the network/aggregate is then predicted using combinatorial arguments. Whilst there is some scepticism in the scientific community pertaining to the proposed mechanism of thermal fragmentation,we have presented compelling evidence in this thesis supporting the currently proposed mechanism and shown that our models can accurately match experimental results. This was achieved using a realistic simulation of the fragmentation of the fractal carbonaceous aggregate structure using our models. Furthermore, in this thesis a method of manipulation using acoustic standing waves is investigated. In our investigation we analysed the effect of frequency and particle size on the ability for the particle to be manipulated by means of a standing acoustic wave. In our results, we report the existence of a critical frequency for a particular particle size. This frequency is inversely proportional to the Stokes time of the particle in the fluid. We also find that for large frequencies the subtle Brownian motion of even larger particles plays a significant role in the efficacy of the manipulation. This is due to the decreasing size of the boundary layer between acoustic nodes. Our model utilises a multiple time scale approach to calculating the long term effects of the standing acoustic field on the particles that are interacting with the sound. These effects are then combined with the effects of Brownian motion in order to obtain a complete mathematical description of the particle dynamics in such acoustic fields. Finally, in this thesis, we develop a numerical routine for the description of "thermal tweezers". Currently, the technique of thermal tweezers is predominantly theoretical however there has been a handful of successful experiments which demonstrate the effect it practise. Thermal tweezers is the name given to the way in which particles can be easily manipulated on a lattice surface by careful selection of a heat distribution over the surface. Typically, the theoretical simulations of the effect can be rather time consuming with supercomputer facilities processing data over days or even weeks. Our alternative numerical method for the simulation of particle distributions pertaining to the thermal tweezers effect use the Fokker-Planck equation to derive a quick numerical method for the calculation of the effective diffusion constant as a result of the lattice and the temperature. We then use this diffusion constant and solve the diffusion equation numerically using the finite volume method. This saves the algorithm from calculating many individual particle trajectories since it is describes the flow of the probability distribution of particles in a continuous manner. The alternative method that is outlined in this thesis can produce a larger quantity of accurate results on a household PC in a matter of hours which is much better than was previously achieveable.

Reliability analysis with suspended items

Reliability analysis has several important engineering applications. Designers and operators of equipment are often interested in the probability of the equipment operating successfully to a given age - this probability is known as the equipment's reliability at that age. Reliability information is also important to those charged with maintaining an item of equipment, as it enables them to model and evaluate alternative maintenance policies for the equipment. In each case, information on failures and survivals of a typical sample of items is used to estimate the required probabilities as a function of the item's age, this process being one of many applications of the statistical techniques known as distribution fitting. In most engineering applications, the estimation procedure must deal with samples containing survivors (suspensions or censorings); this thesis focuses on several graphical estimation methods that are widely used for analysing such samples. Although these methods have been current for many years, they share a common shortcoming: none of them is continuously sensitive to changes in the ages of the suspensions, and we show that the resulting reliability estimates are therefore more pessimistic than necessary. We use a simple example to show that the existing graphical methods take no account of any service recorded by suspensions beyond their respective previous failures, and that this behaviour is inconsistent with one's intuitive expectations. In the course of this thesis, we demonstrate that the existing methods are only justified under restricted conditions. We present several improved methods and demonstrate that each of them overcomes the problem described above, while reducing to one of the existing methods where this is justified. Each of the improved methods thus provides a realistic set of reliability estimates for general (unrestricted) censored samples. Several related variations on these improved methods are also presented and justified. - i