992 resultados para INORGANIC PARTICLES
Resumo:
This thesis describes outcomes of a research study conducted to investigate the nutrient build-up and wash-off processes on urban impervious surfaces. The data needed for the study was generated through a series of field investigations and laboratory test procedures. The study sites were selected in urbanised catchments to represent typical characteristics of residential, industrial and commercial land uses. The build-up and wash-off samples were collected from road surfaces in the selected study sites. A specially designed vacuum collection system and a rainfall simulator were used for sample collection. According to the data analysis, the solids build-up on road surfaces was significantly finer with more than 80% of the particles below 150 ìm for all the land uses. Nutrients were mostly associated with the particle size range below 150 ìm in both build-up and wash-off samples irrespective of type of land use. Therefore, the finer fraction of solids was the most important for the nutrient build-up and particulate nutrient wash-off processes. Consequently, the design of stormwater quality mitigation measures should target particles less than 150 ìm for the removal of nutrients irrespective of type of land use. Total kjeldahl nitrogen (TKN) was the most dominant form of nitrogen species in build-up on road surfaces. Phosphorus build-up on road surfaces was mainly in inorganic form and phosphate (PO4 3-) was the most dominant form. The nutrient wash-off process was found to be dependent on rainfall intensity and duration. Concentration of both total nitrogen and phosphorus was higher at the beginning of the rain event and decreased with the increase in rainfall duration. Consequently, in the design of stormwater quality mitigation strategies for nutrients removal, it is important to target the initial period of rain events. The variability of wash-off of nitrogen with rainfall intensity was significantly different to phosphorus wash-off. The concentration of nitrogen was higher in the wash-off for low intensity rain events compared to the wash-off for high intensity rain events. On the other hand, the concentration of phosphorus in the wash-off was high for high intensity rain events compared to low intensity rain events. Consequently, the nitrogen washoff can be defined as a source limiting process and phosphorus wash-off as a transport limiting process. This highlights the importance of taking into consideration the wash-off of low intensity rain events in the design of stormwater quality mitigation strategies targeting the nitrogen removal. All the nitrogen species in wash-off are primarily in dissolved form whereas phosphorus is in particulate form. The differences in the nitrogen and phosphorus wash-off processes is principally due to the degree of solubility, attachment to particulates, composition of total nitrogen and total phosphorus and the degree of adherence of the solids particles to the surface to which nutrients are attached. The particulate nitrogen available for wash-off is removed readily as these are mobilised as free solids particles on the surface. Phosphorus is washed-off mostly with the solids particles which are strongly adhered to the surface or as the fixed solids load. Investigation of the nitrogen wash-off process using bulk wash-off samples was in close agreement with the investigation of dissolved fraction of wash-off solids. This was primarily due to the predominant nature of dissolved nitrogen. However, the investigation of the processes which underpin phosphorus wash-off using bulk washoff samples could lead to loss of information. This is due to the composition of total phosphorus in wash-off solids and the inherent variability of the wash-off process for the different particle size ranges. This variability should preferably be taken into consideration as phosphorus wash-off is predominantly in particulate form. Therefore, care needs to be taken in the investigation of the phosphorus wash-off process using bulk wash-off samples to ensure that there is no loss of information and hence result in misleading outcomes. The investigation of different particle size ranges of wash-off solids is preferable in the interest of designing effective stormwater quality management strategies targeting phosphorus removal.
Resumo:
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.
Resumo:
Cardiovascular diseases refer to the class of diseases that involve the heart or blood vessels (arteries and veins). Examples of medical devices for treating the cardiovascular diseases include ventricular assist devices (VADs), artificial heart valves and stents. Metallic biomaterials such as titanium and its alloy are commonly used for ventricular assist devices. However, titanium and its alloy show unacceptable thrombosis, which represents a major obstacle to be overcome. Polyurethane (PU) polymer has better blood compatibility and has been used widely in cardiovascular devices. Thus one aim of the project was to coat a PU polymer onto a titanium substrate by increasing the surface roughness, and surface functionality. Since the endothelium of a blood vessel has the most ideal non-thrombogenic properties, it was the target of this research project to grow an endothelial cell layer as a biological coating based on the tissue engineering strategy. However, seeding endothelial cells on the smooth PU coating surfaces is problematic due to the quick loss of seeded cells which do not adhere to the PU surface. Thus it was another aim of the project to create a porous PU top layer on the dense PU pre-layer-coated titanium substrate. The method of preparing the porous PU layer was based on the solvent casting/particulate leaching (SCPL) modified with centrifugation. Without the step of centrifugation, the distribution of the salt particles was not uniform within the polymer solution, and the degree of interconnection between the salt particles was not well controlled. Using the centrifugal treatment, the pore distribution became uniform and the pore interconnectivity was improved even at a high polymer solution concentration (20%) as the maximal salt weight was added in the polymer solution. The titanium surfaces were modified by alkli and heat treatment, followed by functionlisation using hydrogen peroxide. A silane coupling agent was coated before the application of the dense PU pre-layer and the porous PU top layer. The ability of the porous top layer to grow and retain the endothelial cells was also assessed through cell culture techniques. The bonding strengths of the PU coatings to the modified titanium substrates were measured and related to the surface morphologies. The outcome of the project is that it has laid a foundation to achieve the strategy of endothelialisation for the blood compatibility of medical devices. This thesis is divided into seven chapters. Chapter 2 describes the current state of the art in the field of surface modification in cardiovascular devices such as ventricular assist devices (VADs). It also analyses the pros and cons of the existing coatings, particularly in the context of this research. The surface coatings for VADs have evolved from early organic/ inorganic (passive) coatings, to bioactive coatings (e.g. biomolecules), and to cell-based coatings. Based on the commercial applications and the potential of the coatings, the relevant review is focused on the following six types of coatings: (1) titanium nitride (TiN) coatings, (2) diamond-like carbon (DLC) coatings, (3) 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer coatings, (4) heparin coatings, (5) textured surfaces, and (6) endothelial cell lining. Chapter 3 reviews the polymer scaffolds and one relevant fabrication method. In tissue engineering, the function of a polymeric material is to provide a 3-dimensional architecture (scaffold) which is typically used to accommodate transplanted cells and to guide their growth and the regeneration of tissue. The success of these systems is dependent on the design of the tissue engineering scaffolds. Chapter 4 describes chemical surface treatments for titanium and titanium alloys to increase the bond strength to polymer by altering the substrate surface, for example, by increasing surface roughness or changing surface chemistry. The nature of the surface treatment prior to bonding is found to be a major factor controlling the bonding strength. By increasing surface roughness, an increase in surface area occurs, which allows the adhesive to flow in and around the irregularities on the surface to form a mechanical bond. Changing surface chemistry also results in the formation of a chemical bond. Chapter 5 shows that bond strengths between titanium and polyurethane could be significantly improved by surface treating the titanium prior to bonding. Alkaline heat treatment and H2O2 treatment were applied to change the surface roughness and the surface chemistry of titanium. Surface treatment increases the bond strength by altering the substrate surface in a number of ways, including increasing the surface roughness and changing the surface chemistry. Chapter 6 deals with the characterization of the polyurethane scaffolds, which were fabricated using an enhanced solvent casting/particulate (salt) leaching (SCPL) method developed for preparing three-dimensional porous scaffolds for cardiac tissue engineering. The enhanced method involves the combination of a conventional SCPL method and a step of centrifugation, with the centrifugation being employed to improve the pore uniformity and interconnectivity of the scaffolds. It is shown that the enhanced SCPL method and a collagen coating resulted in a spatially uniform distribution of cells throughout the collagen-coated PU scaffolds.In Chapter 7, the enhanced SCPL method is used to form porous features on the polyurethane-coated titanium substrate. The cavities anchored the endothelial cells to remain on the blood contacting surfaces. It is shown that the surface porosities created by the enhanced SCPL may be useful in forming a stable endothelial layer upon the blood contacting surface. Chapter 8 finally summarises the entire work performed on the fabrication and analysis of the polymer-Ti bonding, the enhanced SCPL method and the PU microporous surface on the metallic substrate. It then outlines the possibilities for future work and research in this area.
Resumo:
Alginate microspheres are considered a promising material as a drug carrier in bone repair due to excellent biocompatibility, but their main disadvantage is low drug entrapment efficiency and non-controllable release. The aim of this study was to investigate the effect of incorporating mesoporous bioglass (MBG), non-mesoporous bioglass (BG) or hydroxyapatite (HAp) into alginate microspheres on their drug-loading and release properties. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and atomic emission spectroscopy (AES) were used to analyse the composition, structure and dissolution of bioactive inorganic materials and their microspheres. Dexamethasone (DEX)-loading and release ability of four microspheres were tested in phosphate buffered saline with varying pHs. Results showed that the drug-loading capacity was enhanced with the incorporation of bioactive inorganic materials into alginate microspheres. The MBG/Alginate microspheres had the highest drug loading ability. DEX release from alginate microspheres correlated to the dissolution of MBG, BG and HAp in PBS, and that the pH was an efficient factor in controlling the DEX release; a high pH resulted in greater DEX release, whereas a low pH delayed DEX release. In addition, MBG/alginate, BG/alginate and HAp/alginate microspheres had varying apatite-formation and dissolution abilities, which indicate that the composites would behave differently with respect to bioactivity. The study suggests that microspheres made of a composite of bioactive inorganic materials and alginate have a bioactivity and degradation profile which greatly improves their drug delivery capacity, thus enhancing their potential applications as bioactive filler materials for bone tissue regeneration.
Resumo:
The influence of biogenic particle formation on climate is a well recognised phenomenon. To understand the mechanisms underlying the biogenic particle formation, determining the chemical composition of the new particles and therefore the species that drive the particle production is of utmost importance. Due to the very small amount of mass involved, indirect approaches are frequently used to infer the composition. We present here the results of such an indirect approach by simultaneously measuring volatile and hygroscopic properties of newly formed particles in a forest environment. It is shown that the particles are composed of both sulphates and organics, with the amount of sulphate component strongly depending on the available gas-phase sulphuric acid, and the organic components having the same volatility and hygroscopicity as photooxidation products of a monoterpene such as α-pinene. Our findings agree with a two-step process through nucleation and cluster formation followed by simultaneous growth by condensation of sulphates and organics that take the particles to climatically relevant sizes.
Resumo:
The link between measured sub-saturated hygroscopicity and cloud activation potential of secondary organic aerosol particles produced by the chamber photo-oxidation of α-pinene in the presence or absence of ammonium sulphate seed aerosol was investigated using two models of varying complexity. A simple single hygroscopicity parameter model and a more complex model (incorporating surface effects) were used to assess the detail required to predict the cloud condensation nucleus (CCN) activity from the subsaturated water uptake. Sub-saturated water uptake measured by three hygroscopicity tandem differential mobility analyser (HTDMA) instruments was used to determine the water activity for use in the models. The predicted CCN activity was compared to the measured CCN activation potential using a continuous flow CCN counter. Reconciliation using the more complex model formulation with measured cloud activation could be achieved widely different assumed surface tension behavior of the growing droplet; this was entirely determined by the instrument used as the source of water activity data. This unreliable derivation of the water activity as a function of solute concentration from sub-saturated hygroscopicity data indicates a limitation in the use of such data in predicting cloud condensation nucleus behavior of particles with a significant organic fraction. Similarly, the ability of the simpler single parameter model to predict cloud activation behaviour was dependent on the instrument used to measure sub-saturated hygroscopicity and the relative humidity used to provide the model input. However, agreement was observed for inorganic salt solution particles, which were measured by all instruments in agreement with theory. The difference in HTDMA data from validated and extensively used instruments means that it cannot be stated with certainty the detail required to predict the CCN activity from sub-saturated hygroscopicity. In order to narrow the gap between measurements of hygroscopic growth and CCN activity the processes involved must be understood and the instrumentation extensively quality assured. It is impossible to say from the results presented here due to the differences in HTDMA data whether: i) Surface tension suppression occurs ii) Bulk to surface partitioning is important iii) The water activity coefficient changes significantly as a function of the solute concentration.
Resumo:
Airborne measurements of particle number concentrations from biomass burning were conducted in the Northern Territory, Australia, during June and September campaigns in 2003, which is the early and the late dry season in that region. The airborne measurements were performed along horizontal flight tracks, at several heights in order to gain insight into the particle concentration levels and their variation with height within the lower boundary layer (LBL), upper boundary layer (UBL), and also in the free troposphere (FT). The measurements found that the concentration of particles during the early dry season was lower than that for the late dry season. For the June campaign, the concentration of particles in LBL, UBL, and FT were (685 ± 245) particles/cm3, (365 ± 183) particles/cm3, and (495 ± 45) particle/cm3 respectively. For the September campaign, the concentration of particles were found to be (1233 ± 274) particles/cm3 in the LBL, (651 ± 68) particles/cm3 in the UBL, and (568 ± 70) particles/cm3 in the FT. The particle size distribution measurements indicate that during the late dry season there was no change in the particle size distribution below (LBL) and above the boundary layer (UBL). This indicates that there was possibly some penetration of biomass burning particles into the upper boundary layer. In the free troposphere the particle concentration and size measured during both campaigns were approximately the same.
Resumo:
Concentrations of ultrafine (<0.1µm) particles (UFPs) and PM2.5 (<2.5µm) were measured whilst commuting along a similar route by train, bus, ferry and automobile in Sydney, Australia. One trip on each transport mode was undertaken during both morning and evening peak hours throughout a working week, for a total of 40 trips. Analyses comprised one-way ANOVA to compare overall (i.e. all trips combined) geometric mean concentrations of both particle fractions measured across transport modes, and assessment of both the correlation between wind speed and individual trip means of UFPs and PM2.5, and the correlation between the two particle fractions. Overall geometric mean concentrations of UFPs and PM2.5 ranged from 2.8 (train) to 8.4 (bus) × 104 particles cm-3 and 22.6 (automobile) to 29.6 (bus) µg m-3, respectively, and a statistically significant difference (p <0.001) between modes was found for both particle fractions. Individual trip geometric mean concentrations were between 9.7 × 103 (train) and 2.2 × 105 (bus) particles cm-3 and 9.5 (train) to 78.7 (train) µg m-3. Estimated commuter exposures were variable, and the highest return trip mean PM2.5 exposure occurred in the ferry mode, whilst the highest UFP exposure occurred during bus trips. The correlation between fractions was generally poor, and in keeping with the duality of particle mass and number emissions in vehicle-dominated urban areas. Wind speed was negatively correlated with, and a generally poor determinant of, UFP and PM2.5 concentrations, suggesting a more significant role for other factors in determining commuter exposure.
Resumo:
This study reports the potential toxicological impact of particles produced during biomass combustion by an automatic pellet boiler and a traditional logwood stove under various combustion conditions using a novel profluorescent nitroxide probe BPEAnit. This probe is weakly fluorescent, but yields strong fluorescence emission upon radical trapping or redox activity. Samples were collected by bubbling aerosol through an impinger containing BPEAnit solution, followed by fluorescence measurement. The fluorescence of BPEAnit was measured for particles produced during various combustion phases, at the beginning of burning (cold start), stable combustion after refilling with the fuel (warm start) and poor burning conditions. For particles produced by the logwood stove under cold-start conditions significantly higher amounts of reactive species per unit of particulate mass were observed compared to emissions produced during a warm start. In addition, sampling of logwood burning emissions after passing through a thermodenuder at 250oC resulted in an 80-100% reduction of the fluorescence signal of BPEAnit probe, indicating that the majority of reactive species were semivolatile. Moreover, the amount of reactive species showed a strong correlation with the amount of particulate organic material. This indicates the importance of semivolatile organics in particle-related toxicity. Particle emissions from the pellet boiler, although of similar mass concentration, were not observed to lead to an increase in fluorescence signal during any of the combustion phases.
Resumo:
Much has been written about airborne particulate matter, and countless meetings, workshops and conferences have been held, both nationally and internationally, to address the many scientific challenges which they present, especially when one considers their effects on human health. Particles are a complex airborne pollutant, because of their many different characteristics and the many different ways in which they can be measured and detected. This article summarises the current state of knowledge on the effects of particulate matter and health, based primarily on epidemiological studies which focused on exposure to particle mass, and more recently, on particle number concentration.
Resumo:
The multi-criteria decision making methods, Preference METHods for Enrichment Evaluation (PROMETHEE) and Graphical Analysis for Interactive Assistance (GAIA), and the two-way Positive Matrix Factorization (PMF) receptor model were applied to airborne fine particle compositional data collected at three sites in Hong Kong during two monitoring campaigns held from November 2000 to October 2001 and November 2004 to October 2005. PROMETHEE/GAIA indicated that the three sites were worse during the later monitoring campaign, and that the order of the air quality at the sites during each campaign was: rural site > urban site > roadside site. The PMF analysis on the other hand, identified 6 common sources at all of the sites (diesel vehicle, fresh sea salt, secondary sulphate, soil, aged sea salt and oil combustion) which accounted for approximately 68.8 ± 8.7% of the fine particle mass at the sites. In addition, road dust, gasoline vehicle, biomass burning, secondary nitrate, and metal processing were identified at some of the sites. Secondary sulphate was found to be the highest contributor to the fine particle mass at the rural and urban sites with vehicle emission as a high contributor to the roadside site. The PMF results are broadly similar to those obtained in a previous analysis by PCA/APCS. However, the PMF analysis resolved more factors at each site than the PCA/APCS. In addition, the study demonstrated that combined results from multi-criteria decision making analysis and receptor modelling can provide more detailed information that can be used to formulate the scientific basis for mitigating air pollution in the region.
Resumo:
Closteroviruslike particles, designated as grapevine corky bark-associated virus (GCBaV), were purified from mature leaves and stem phloem tissue of a corky bark-affected grapevine that had indexed negative for other grapevine viruses. Electron microscopy of purified preparations revealed the presence of flexuous rod-shaped viruslike particles that were about 13 nm in diameter and between 1,400 and 2,000 nm long, with a helical pitch of 3.4 nm. In purified preparations, the GCBaV particles degraded within a few weeks, unlike grapevine leafroll associated virus (GLRaV), which was stable for more than 1 mo under the same storage condition. The molecular weight of the coat protein of GCBaV was 24,000. A large dsRNA molecule (about 15.3 kbp), along with lower molecular weight species, was detected in tissues of corky bark-diseased grapevines, but not in healthy grapevines. Polyclonal antisera were produced in rabbits against purified or partially purified virus preparations. In direct enzyme-linked immunosorbent assay (ELISA), antisera to GCBaV did not react to the serologically distinct types (II and III) of the long closteroviruses associated with grapevine leafroll disease and grapevine virus A (GVA), and vice versa. This antiserum also reacted in ELISA with other corky bark-affected grapevines. Our data suggest that closteroviruslike particles, designated as GCBaV, may be the causal agent of corky bark disease. However, definitive proof is still lacking. The inclusion of GCBaV in the group of closteroviruses with citrus tristeza virus is proposed.
Resumo:
Airborne fine particles were collected at a suburban site in Queensland, Australia between 1995 and 2003. The samples were analysed for 21 elements, and Positive Matrix Factorisation (PMF), Preference Ranking Organisation METHods for Enrichment Evaluation (PROMETHEE) and Graphical Analysis for Interactive Assistance (GAIA) were applied to the data. PROMETHEE provided information on the ranking of pollutant levels from the sampling years while PMF provided insights into the sources of the pollutants, their chemical composition, most likely locations and relative contribution to the levels of particulate pollution at the site. PROMETHEE and GAIA found that the removal of lead from fuel in the area had a significant impact on the pollution patterns while PMF identified 6 pollution sources including: Railways (5.5%), Biomass Burning (43.3%), Soil (9.2%), Sea Salt (15.6%), Aged Sea Salt (24.4%) and Motor Vehicles (2.0%). Thus the results gave information that can assist in the formulation of mitigation measures for air pollution.
Resumo:
An ethylenediamine-assisted route has been designed for one-step synthesis of lithium niobate particles with a novel rodlike structure in an aqueous solution system. The morphological evolution for these lithium niobate rods was monitored via SEM: The raw materials form large lozenges first. These lozenges are a metastable intermediate of this reaction, and they subsequently crack into small rods after sufficiently long time. These small rods recrystallize and finally grow into individual lithium niobate rods. Interestingly, shape-controlled fabrication of lithium niobate powders was achieved through using different amine ligands. For instance, the ethylenediamine or ethanolamine ligan can induce the formation of rods, while n-butylamine prefers to construct hollow spheres. These as-obtained lithium niobate rods and hollow spheres may exhibit enhanced performance in an optical application field due to their distinctive structures. This effective ligand-tuned-morphology route can provide a new strategy to facilely achieve the shape-controlled synthesis of other niobates.