Exposure to particles from laser printers operating within office workplaces

While recent research has provided valuable information as to the composition of laser printer particles, their formation mechanisms, and explained why some printers are emitters whilst others are low emitters, fundamental questions relating to the potential exposure of office workers remained unanswered. In particular, (i) what impact does the operation of laser printers have on the background particle number concentration (PNC) of an office environment over the duration of a typical working day?; (ii) what is the airborne particle exposure to office workers in the vicinity of laser printers; (iii) what influence does the office ventilation have upon the transport and concentration of particles?; (iv) is there a need to control the generation of, and/or transport of particles arising from the operation of laser printers within an office environment?; (v) what instrumentation and methodology is relevant for characterising such particles within an office location? We present experimental evidence on printer temporal and spatial PNC during the operation of 107 laser printers within open plan offices of five buildings. We show for the first time that the eight-hour time-weighted average printer particle exposure is significantly less than the eight-hour time-weighted local background particle exposure, but that peak printer particle exposure can be greater than two orders of magnitude higher than local background particle exposure. The particle size range is predominantly ultrafine (< 100nm diameter). In addition we have established that office workers are constantly exposed to non-printer derived particle concentrations, with up to an order of magnitude difference in such exposure amongst offices, and propose that such exposure be controlled along with exposure to printer derived particles. We also propose, for the first time, that peak particle reference values be calculated for each office area analogous to the criteria used in Australia and elsewhere for evaluating exposure excursion above occupational hazardous chemical exposure standards. A universal peak particle reference value of 2.0 x 104 particles cm-3 has been proposed.

Is adiponectin implicated in venous thromboembolism?

In summary, these results imply that the relationship of adiponectin with lipoproteins is more complex than previously predicted using other methods of lipoprotein fractionation. Higher correlation of adiponectin was shown with large lipoprotein particle size, independent of the apolipoprotein content. Given the small population studied, we could not assess the influence of mild risk factors for venous thrombosis, such as obesity, on the analysis of the results. Thus, we can only state that adiponectin levels appear not to be a strong risk factor for VTE. It is possible that adiponectin deficiency may contribute indirectly to the etiology of VTE by enhancing the inflammatory state. © 2006 International Society on Thrombosis and Haemostasis.

Characteristics of airborne ultrafine and coarse particles during the Australian dust storm of 23 September 2009

Particle number concentrations and size distributions, visibility and particulate mass concentrations and weather parameters were monitored in Brisbane, Australia, on 23 September 2009, during the passage of a dust storm that originated 1400 km away in the dry continental interior. The dust concentration peaked at about mid-day when the hourly average PM2.5 and PM10 values reached 814 and 6460 µg m-3, respectively, with a sharp drop in atmospheric visibility. A linear regression analysis showed a good correlation between the coefficient of light scattering by particles (Bsp) and both PM10 and PM2.5. The particle number in the size range 0.5-20 µm exhibited a lognormal size distribution with modal and geometrical mean diameters of 1.6 and 1.9 µm, respectively. The modal mass was around 10 µm with less than 10% of the mass carried by particles smaller than 2.5 µm. The PM10 fraction accounted for about 68% of the total mass. By mid-day, as the dust began to increase sharply, the ultrafine particle number concentration fell from about 6x103 cm-3 to 3x103 cm-3 and then continued to decrease to less than 1x103 cm-3 by 14h, showing a power-law decrease with Bsp with an R2 value of 0.77 (p<0.01). Ultrafine particle size distributions also showed a significant decrease in number during the dust storm. This is the first scientific study of particle size distributions in an Australian dust storm.

Investigation of the effect of organics on the water uptake of marine aerosols

Water uptake refers to the ability of atmospheric particles to take up water vapour from the surrounding atmosphere. This is an important property that affects particle size and phase and therefore influences many characteristics of aerosols relevant to air quality and climate. However, the water uptake properties of many important atmospheric aerosol systems, including those related to the oceans, are still not fully understood. Therefore, the primary aim of this PhD research program was to investigate the water uptake properties of marine aerosols. In particular, the effect of organics on marine aerosol water uptake was investigated. Field campaigns were conducted at remote coastal sites on the east coast of Australia (Agnes Water; March-April 2007) and west coast of Ireland (Mace Head; June 2007), and laboratory measurements were performed on bubble-generated sea spray aerosols. A combined Volatility-Hygroscopicity-Tandem Differential Mobility Analyser (VH-TDMA) was employed in all experiments. This system probes the changes in the hygroscopic properties of nanoparticles as volatile organic components are progressively evaporated. It also allows particle composition to be inferred from combined volatility-hygroscopicity measurements. Frequent new particle formation and growth events were observed during the Agnes Water campaign. The VH-TDMA was used to investigate freshly nucleated particles (17-22.5 nm) and it was found that the condensation of sulphate and/or organic vapours was responsible for driving particle growth during the events. Aitken mode particles (~40 nm) were also measured with the VH-TDMA. In 3 out of 18 VH-TDMA scans evaporation of a volatile, organic component caused a very large increase in hygroscopicity that could only be explained by an increase in the absolute water uptake of the particle residuals, and not merely an increase in their relative hygroscopicity. This indicated the presence of organic components that were suppressing the hygroscopic growth of mixed particles on the timescale of humidification in the VH-TDMA (6.5 secs). It was suggested that the suppression of water uptake was caused by either a reduced rate of hygroscopic growth due to the presence of organic films, or organic-inorganic interactions in solution droplets that had a negative effect on hygroscopicity. Mixed organic-inorganic particles were rarely observed by the VH-TDMA during the summer campaign conducted at Mace Head. The majority of particles below 100 nm in clean, marine air appeared to be sulphates neutralised to varying degrees by ammonia. On one unique day, 26 June 2007, particularly large concentrations of sulphate aerosol were observed and identified as volcanic emissions from Iceland. The degree of neutralisation of the sulphate aerosol by ammonia was calculated by the VH-TDMA and found to compare well with the same quantity measured by an aerosol mass spectrometer. This was an important verification of the VH-TMDA‘s ability to identify ammoniated sulphate aerosols based on the simultaneous measurement of aerosol volatility and hygroscopicity. A series of measurements were also conducted on sea spray aerosols generated from Moreton Bay seawater samples in a laboratory-based bubble chamber. Accumulation mode sea spray particles (38-173 nm) were found to contain only a minor organic fraction (< 10%) that had little effect on particle hygroscopicity. These results are important because previous studies have observed that accumulation mode sea spray particles are predominantly organic (~80% organic mass fraction). The work presented here suggests that this is not always the case, and that there may be currently unknown factors that are controlling the transfer of organics to the aerosol phase during the bubble bursting process. Taken together, the results of this research program have significantly improved our understanding of organic-containing marine aerosols and the way they interact with water vapour in the atmosphere.

Influence of physical and chemical properties of solids on heavy metal adsorption

Partition of heavy metals between particulate and dissolve fraction of stormwater primarily depends on the adsorption characteristics of solids particles. Moreover, the bioavailability of heavy metals is also influenced by the adsorption behaviour of solids. However, due to the lack of fundamental knowledge in relation to the heavy metals adsorption processes of road deposited solids, the effectiveness of stormwater management strategies can be limited. The research study focused on the investigation of the physical and chemical parameters of solids on urban road surfaces and, more specifically, on heavy metal adsorption to solids. Due to the complex nature of heavy metal interaction with solids, a substantial database was generated through a series of field investigations and laboratory experiments. The study sites for the build-up pollutant sample collection were selected from four urbanised suburbs located in a major river catchment. Sixteen road sites were selected from these suburbs and represented typical industrial, commercial and residential land uses. Build-up pollutants were collected using a wet and dry vacuum collection technique which was specially designed to improve fine particle collection. Roadside soil samples were also collected from each suburb for comparison with the road surface solids. The collected build-up solids samples were separated into four particle size ranges and tested for a range of physical and chemical parameters. The solids build-up on road surfaces contained a high fraction (70%) of particles smaller than 150ìm, which are favourable for heavy metal adsorption. These solids particles predominantly consist of soil derived minerals which included quartz, albite, microcline, muscovite and chlorite. Additionally, a high percentage of amorphous content was also identified in road deposited solids. In comparing the mineralogical data of surrounding soil and road deposited solids, it was found that about 30% of the solids consisted of particles generated from traffic related activities on road surfaces. Significant difference in mineralogical composition was noted in different particle sizes of build-up solids. Fine solids particles (<150ìm) consisted of a clayey matrix and high amorphous content (in the region of 40%) while coarse particles (>150ìm) consisted of a sandy matrix at all study sites, with about 60% quartz content. Due to these differences in mineralogical components, particles larger than and smaller than 150ìm had significant differences in their specific surface area (SSA) and effective cation exchange capacity (ECEC). These parameters, in turn, exert a significant influence on heavy metal adsorption. Consequently, heavy metal content in >150ìm particles was lower than in the case of fine particles. The particle size range <75ìm had the highest heavy metal content, corresponding with its high clay forming minerals, high organic matter and low quartz content which increased the SSA, ECEC and the presence of Fe, Al and Mn oxides. The clay forming minerals, high organic matter and Fe, Al and Mn oxides create distinct groups of charge sites on solids surfaces and exhibit different adsorption mechanisms and bond strength, between heavy metal elements and charge sites. Therefore, the predominance of these factors in different particle sizes leads to different heavy metal adsorption characteristics. Heavy metals show preference for association with clay forming minerals in fine solids particles, whilst in coarse particles heavy metals preferentially associate with organic matter. Although heavy metal adsorption to amorphous material is very low, the heavy metals embedded in traffic related materials have a potential impact on stormwater quality.Adsorption of heavy metals is not confined to an individual type of charge site in solids, whereas specific heavy metal elements show preference for adsorption to several different types of charge sites in solids. This is attributed to the dearth of preferred binding sites and the inability to reach the preferred binding sites due to competition between different heavy metal species. This confirms that heavy metal adsorption is significantly influenced by the physical and chemical parameters of solids that lead to a heterogeneity of surface charge sites. The research study highlighted the importance of removal of solids particles from stormwater runoff before they enter into receiving waters to reduce the potential risk posed by the bioavailability of heavy metals. The bioavailability of heavy metals not only results from the easily mobile fraction bound to the solids particles, but can also occur as a result of the dissolution of other forms of bonds by chemical changes in stormwater or microbial activity. Due to the diversity in the composition of the different particle sizes of solids and the characteristics and amount of charge sites on the particle surfaces, investigations using bulk solids are not adequate to gain an understanding of the heavy metal adsorption processes of solids particles. Therefore, the investigation of different particle size ranges is recommended for enhancing stormwater quality management practices.

Formation mechanisms of secondary organic aerosols in relation to laser printer emissions

Due to their large surface area, complex chemical composition and high alveolar deposition rate, ultrafine particles (UFPs) (< 0.1 ìm) pose a significant risk to human health and their toxicological effects have been acknowledged by the World Health Organisation. Since people spend most of their time indoors, there is a growing concern about the UFPs present in some indoor environments. Recent studies have shown that office machines, in particular laser printers, are a significant indoor source of UFPs. The majority of printer-generated UFPs are organic carbon and it is unlikely that these particles are emitted directly from the printer or its supplies (such as paper and toner powder). Thus, it was hypothesised that these UFPs are secondary organic aerosols (SOA). Considering the widespread use of printers and human exposure to these particles, understanding the processes involved in particle formation is of critical importance. However, few studies have investigated the nature (e.g. volatility, hygroscopicity, composition, size distribution and mixing state) and formation mechanisms of these particles. In order to address this gap in scientific knowledge, a comprehensive study including state-of-art instrumental methods was conducted to characterise the real-time emissions from modern commercial laser printers, including particles, volatile organic compounds (VOCs) and ozone (O3). The morphology, elemental composition, volatility and hygroscopicity of generated particles were also examined. The large set of experimental results was analysed and interpreted to provide insight into: (1) Emissions profiles of laser printers: The results showed that UFPs dominated the number concentrations of generated particles, with a quasi unimodal size distribution observed for all tests. These particles were volatile, non-hygroscopic and mixed both externally and internally. Particle microanalysis indicated that semi-volatile organic compounds occupied the dominant fraction of these particles, with only trace quantities of particles containing Ca and Fe. Furthermore, almost all laser printers tested in this study emitted measurable concentrations of VOCs and O3. A positive correlation between submicron particles and O3 concentrations, as well as a contrasting negative correlation between submicron particles and total VOC concentrations were observed during printing for all tests. These results proved that UFPs generated from laser printers are mainly SOAs. (2) Sources and precursors of generated particles: In order to identify the possible particle sources, particle formation potentials of both the printer components (e.g. fuser roller and lubricant oil) and supplies (e.g. paper and toner powder) were investigated using furnace tests. The VOCs emitted during the experiments were sampled and identified to provide information about particle precursors. The results suggested that all of the tested materials had the potential to generate particles upon heating. Nine unsaturated VOCs were identified from the emissions produced by paper and toner, which may contribute to the formation of UFPs through oxidation reactions with ozone. (3) Factors influencing the particle emission: The factors influencing particle emissions were also investigated by comparing two popular laser printers, one showing particle emissions three orders of magnitude higher than the other. The effects of toner coverage, printing history, type of paper and toner, and working temperature of the fuser roller on particle number emissions were examined. The results showed that the temperature of the fuser roller was a key factor driving the emission of particles. Based on the results for 30 different types of laser printers, a systematic positive correlation was observed between temperature and particle number emissions for printers that used the same heating technology and had a similar structure and fuser material. It was also found that temperature fluctuations were associated with intense bursts of particles and therefore, they may have impact on the particle emissions. Furthermore, the results indicated that the type of paper and toner powder contributed to particle emissions, while no apparent relationship was observed between toner coverage and levels of submicron particles. (4) Mechanisms of SOA formation, growth and ageing: The overall hypothesis that UFPs are formed by reactions with the VOCs and O3 emitted from laser printers was examined. The results proved this hypothesis and suggested that O3 may also play a role in particle ageing. In addition, knowledge about the mixing state of generated particles was utilised to explore the detailed processes of particle formation for different printing scenarios, including warm-up, normal printing, and printing without toner. The results indicated that polymerisation may have occurred on the surface of the generated particles to produce thermoplastic polymers, which may account for the expandable characteristics of some particles. Furthermore, toner and other particle residues on the idling belt from previous print jobs were a very clear contributing factor in the formation of laser printer-emitted particles. In summary, this study not only improves scientific understanding of the nature of printer-generated particles, but also provides significant insight into the formation and ageing mechanisms of SOAs in the indoor environment. The outcomes will also be beneficial to governments, industry and individuals.

Influence of rainfall and catchment characteristics on urban stormwater quality

This thesis presents the outcomes of a comprehensive research study undertaken to investigate the influence of rainfall and catchment characteristics on urban stormwater quality. The knowledge created is expected to contribute to a greater understanding of urban stormwater quality and thereby enhance the design of stormwater quality treatment systems. The research study was undertaken based on selected urban catchments in Gold Coast, Australia. The research methodology included field investigations, laboratory testing, computer modelling and data analysis. Both univariate and multivariate data analysis techniques were used to investigate the influence of rainfall and catchment characteristics on urban stormwater quality. The rainfall characteristics investigated included average rainfall intensity and rainfall duration whilst catchment characteristics included land use, impervious area percentage, urban form and pervious area location. The catchment scale data for the analysis was obtained from four residential catchments, including rainfall-runoff records, drainage network data, stormwater quality data and land use and land cover data. Pollutants build-up samples were collected from twelve road surfaces in residential, commercial and industrial land use areas. The relationships between rainfall characteristics, catchment characteristics and urban stormwater quality were investigated based on residential catchments and then extended to other land uses. Based on the influence rainfall characteristics exert on urban stormwater quality, rainfall events can be classified into three different types, namely, high average intensity-short duration (Type 1), high average intensity-long duration (Type 2) and low average intensity-long duration (Type 3). This provides an innovative approach to conventional modelling which does not commonly relate stormwater quality to rainfall characteristics. Additionally, it was found that the threshold intensity for pollutant wash-off from urban catchments is much less than for rural catchments. High average intensity-short duration rainfall events are cumulatively responsible for the generation of a major fraction of the annual pollutants load compared to the other rainfall event types. Additionally, rainfall events less than 1 year ARI such as 6- month ARI should be considered for treatment design as they generate a significant fraction of the annual runoff volume and by implication a significant fraction of the pollutants load. This implies that stormwater treatment designs based on larger rainfall events would not be feasible in the context of cost-effectiveness, efficiency in treatment performance and possible savings in land area needed. This also suggests that the simulation of long-term continuous rainfall events for stormwater treatment design may not be needed and that event based simulations would be adequate. The investigations into the relationship between catchment characteristics and urban stormwater quality found that other than conventional catchment characteristics such as land use and impervious area percentage, other catchment characteristics such as urban form and pervious area location also play important roles in influencing urban stormwater quality. These outcomes point to the fact that the conventional modelling approach in the design of stormwater quality treatment systems which is commonly based on land use and impervious area percentage would be inadequate. It was also noted that the small uniformly urbanised areas within a larger mixed catchment produce relatively lower variations in stormwater quality and as expected lower runoff volume with the opposite being the case for large mixed use urbanised catchments. Therefore, a decentralised approach to water quality treatment would be more effective rather than an "end-of-pipe" approach. The investigation of pollutants build-up on different land uses showed that pollutant build-up characteristics vary even within the same land use. Therefore, the conventional approach in stormwater quality modelling, which is based solely on land use, may prove to be inappropriate. Industrial land use has relatively higher variability in maximum pollutant build-up, build-up rate and particle size distribution than the other two land uses. However, commercial and residential land uses had relatively higher variations of nutrients and organic carbon build-up. Additionally, it was found that particle size distribution had a relatively higher variability for all three land uses compared to the other build-up parameters. The high variability in particle size distribution for all land uses illustrate the dissimilarities associated with the fine and coarse particle size fractions even within the same land use and hence the variations in stormwater quality in relation to pollutants adsorbing to different sizes of particles.

Characterisation and source identification of selected pollutants in house dust

House dust is a heterogeneous matrix, which contains a number of biological materials and particulate matter gathered from several sources. It is the accumulation of a number of semi-volatile and non-volatile contaminants. The contaminants are trapped and preserved. Therefore, house dust can be viewed as an archive of both the indoor and outdoor air pollution. There is evidence to show that on average, people tend to stay indoors most of the time and this increases exposure to house dust. The aims of this investigation were to: " assess the levels of Polycyclic Aromatic Hydrocarbons (PAHs), elements and pesticides in the indoor environment of the Brisbane area; " identify and characterise the possible sources of elemental constituents (inorganic elements), PAHs and pesticides by means of Positive Matrix Factorisation (PMF); and " establish the correlations between the levels of indoor air pollutants (PAHs, elements and pesticides) with the external and internal characteristics or attributes of the buildings and indoor activities by means of multivariate data analysis techniques. The dust samples were collected during the period of 2005-2007 from homes located in different suburbs of Brisbane, Ipswich and Toowoomba, in South East Queensland, Australia. A vacuum cleaner fitted with a paper bag was used as a sampler for collecting the house dust. A survey questionnaire was filled by the house residents which contained information about the indoor and outdoor characteristics of their residences. House dust samples were analysed for three different pollutants: Pesticides, Elements and PAHs. The analyses were carried-out for samples of particle size less than 250 µm. The chemical analyses for both pesticides and PAHs were performed using a Gas Chromatography Mass Spectrometry (GC-MS), while elemental analysis was carried-out by using Inductively-Coupled Plasma-Mass Spectroscopy (ICP-MS). The data was subjected to multivariate data analysis techniques such as multi-criteria decision-making procedures, Preference Ranking Organisation Method for Enrichment Evaluations (PROMETHEE), coupled with Geometrical Analysis for Interactive Aid (GAIA) in order to rank the samples and to examine data display. This study showed that compared to the results from previous works, which were carried-out in Australia and overseas, the concentrations of pollutants in house dusts in Brisbane and the surrounding areas were relatively very high. The results of this work also showed significant correlations between some of the physical parameters (types of building material, floor level, distance from industrial areas and major road, and smoking) and the concentrations of pollutants. Types of building materials and the age of houses were found to be two of the primary factors that affect the concentrations of pesticides and elements in house dust. The concentrations of these two types of pollutant appear to be higher in old houses (timber houses) than in the brick ones. In contrast, the concentrations of PAHs were noticed to be higher in brick houses than in the timber ones. Other factors such as floor level, and distance from the main street and industrial area, also affected the concentrations of pollutants in the house dust samples. To apportion the sources and to understand mechanisms of pollutants, Positive Matrix Factorisation (PMF) receptor model was applied. The results showed that there were significant correlations between the degree of concentration of contaminants in house dust and the physical characteristics of houses, such as the age and the type of the house, the distance from the main road and industrial areas, and smoking. Sources of pollutants were identified. For PAHs, the sources were cooking activities, vehicle emissions, smoking, oil fumes, natural gas combustion and traces of diesel exhaust emissions; for pesticides the sources were application of pesticides for controlling termites in buildings and fences, treating indoor furniture and in gardens for controlling pests attacking horticultural and ornamental plants; for elements the sources were soil, cooking, smoking, paints, pesticides, combustion of motor fuels, residual fuel oil, motor vehicle emissions, wearing down of brake linings and industrial activities.

Role of solids in heavy metals build-up on urban road surfaces

Solids are widely identified as a carrier of harmful pollutants in stormwater runoff exerting a significant risk to receiving waters. This paper outlines the findings of an in-depth investigation on heavy metal adsorption to solids surfaces. Pollutant build-up samples collected from sixteen road sites in residential, industrial and commercial land uses were separated into four particle size ranges and analysed for a range of physico-chemical parameters and nine heavy metals including Iron (Fe), Aluminum (Al), Lead (Pb), Zinc (Zn), Cadmium (Cd), Chromium (Cr), Manganese (Mn), Nickel (Ni) and Copper (Cu). High specific surface area (SSA) and total organic carbon (TOC) content in finer particle size ranges was noted, thus confirming strong correlations with heavy metals. Based on their physico-chemical characteristics, two different types of solids originating from traffic and soil sources were identified. Solids generated by traffic were associated with high loads of heavy metals such as Cd and Cr with strong correlation with SSA. This suggested the existence of surface dependent bonds such as cation exchange between heavy metals and solids. In contrast, Fe, Al and Mn which can be attributed to soil inputs showed strong correlation with TOC suggesting strong bonds such as chemsorption. Zn was found to be primarily attached to solids by bonding with the oxides of Fe, Al and Mn. The data analysis also confirmed the predominance of the finer fraction, with 70% of the solids being finer than 150 µm and containing 60% of the heavy metal pollutant load.

Pyrolysis of coconut shell for bio-oil

The conversion of coconut shell into pyrolytic oil by fixed bed fire-tube heating reactor has been taken into consideration in this study. The major components of the system were fixed bed fire-tube heating reactor, liquid condenser and collectors. The raw and crushed tamarind seed in particle form was pyrolized in an electrically heated 10 cm diameter and 27 cm high fixed bed reactor. The products are oil, char and gases. The parameters varied were reactor bed temperature, running time, gas flow rate and feed particle size. The parameters were found to influence the product yields significantly. The maximum liquid yield was 34.3 wt% at 4500C for a feed size of 0.6mm at a gas flow rate of 6 liter/min with a running time of minute. The pyrolysis oil was obtained at these optimum process conditions were analyzed for physical and chemical properties to be used as an alternative fuel.

Mixing and drying mud and ash at Tully Mill

Disposal of mud and ash, particularly in wet weather conditions, is a significant expense for mills. This paper reports on part of a process to pelletise mud and ash, aimed at making mud and ash more attractive to growers across entire mill districts. The full process and the re-constituting and centrifuging rotary vacuum filter mud part of the process were described in two papers to the 2011 conference. The component described in this paper involves aspects of mixing mud and ash with subsequent drying using boiler exit gas. The mud material needs to mix easily with boiler ash and the mixture has to feed easily into and be pneumatically conveyed by a flue gas dryer. The performance of a pilot flue gas dryer for drying mud and ash was evaluated. The mud and ash mixture was found to dry much faster than final bagasse, provided the mud and ash material was broken up into individual particles. A previously developed computer model of bagasse drying was updated to take into account the smaller particle size of the mud and ash mixture. This upgraded model predicted the performance of the pilot flue gas dryer well.

Experimental and theoretical investigation of ligand effects on the synthesis of ZnO nanoparticles

ZnO nanoparticles with highly controllable particle sizes(less than 10 nm) were synthesized using organic capping ligands in Zn(Ac)2 ethanolic solution. The molecular structure of the ligands was found to have significant influence on the particle size. The multi-functional molecule tris(hydroxymethyl)-aminomethane (THMA) favoured smaller particle distributions compared with ligands possessing long hydrocarbon chains that are more frequently employed. The adsorption of capping ligands on ZnnOn crystal nuclei (where n = 4 or 18 molecular clusters of(0001) ZnO surfaces) was modelled by ab initio methods at the density functional theory (DFT) level. For the molecules examined, chemisorption proceeded via the formation of Zn...O, Zn...N, or Zn...S chemical bonds between the ligands and active Zn2+ sites on ZnO surfaces. The DFT results indicated that THMA binds more strongly to the ZnO surface than other ligands, suggesting that this molecule is very effective at stabilizing ZnO nanoparticle surfaces. This study, therefore, provides new insight into the correlation between the molecular structure of capping ligands and the morphology of metal oxide nanostructures formed in their presence.

Relating vehicle generated pollutants to urban stormwater quality

Rapid urbanisation and resulting continuous increase in traffic has been recognised as key factors in the contribution of increased pollutant loads to urban stormwater and in turn to receiving waters. Urbanisation primarily increases anthropogenic activities and the percentage of impervious surfaces in urban areas. These processes are collectively responsible for urban stormwater pollution. In this regard, urban traffic and land use related activities have been recognised as the primary pollutant sources. This is primarily due to the generation of a range of key pollutants such as solids, heavy metals and PAHs. Appropriate treatment system design is the most viable approach to mitigate stormwater pollution. However, limited understanding of the pollutant process and transport pathways constrains effective treatment design. This highlights necessity for the detailed understanding of traffic and other land use related pollutants processes and pathways in relation to urban stormwater pollution. This study has created new knowledge in relation to pollutant processes and transport pathways encompassing atmospheric pollutants, atmospheric deposition and build-up on ground surfaces of traffic generated key pollutants. The research study was primarily based on in-depth experimental investigations. This thesis describes the extensive knowledge created relating to the processes of atmospheric pollutant build-up, atmospheric deposition and road surface build-up and establishing their relationships as a chain of processes. The analysis of atmospheric deposition revealed that both traffic and land use related sources contribute total suspended particulate matter (TSP) to the atmosphere. Traffic sources become dominant during weekdays whereas land use related sources become dominant during weekends due to the reduction in traffic sources. The analysis further concluded that atmospheric TSP, polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs) concentrations are highly influenced by total average daily heavy duty traffic, traffic congestion and the fraction of commercial and industrial land uses. A set of mathematical equation were developed to predict TSP, PAHs and HMs concentrations in the atmosphere based on the influential traffic and land use related parameters. Dry deposition samples were collected for different antecedent dry days and wet deposition samples were collected immediately after rainfall events. The dry deposition was found to increase with the antecedent dry days and consisted of relatively coarser particles (greater than 1.4 ìm) when compared to wet deposition. The wet deposition showed a strong affinity to rainfall depth, but was not related to the antecedent dry period. It was also found that smaller size particles (less than 1.4 ìm) travel much longer distances from the source and deposit mainly with the wet deposition. Pollutants in wet deposition are less sensitive to the source characteristics compared to dry deposition. Atmospheric deposition of HMs is not directly influenced by land use but rather by proximity to high emission sources such as highways. Therefore, it is important to consider atmospheric deposition as a key pollutant source to urban stormwater in the vicinity of these types of sources. Build-up was analysed for five different particle size fractions, namely, <1 ìm, 1-75 ìm, 75-150 ìm, 150-300 ìm and >300 ìm for solids, PAHs and HMs. The outcomes of the study indicated that PAHs and HMs in the <75 ìm size fraction are generated mainly by traffic related activities whereas the > 150 ìm size fraction is generated by both traffic and land use related sources. Atmospheric deposition is an important source for HMs build-up on roads, whereas the contribution of PAHs from atmospheric sources is limited. A comprehensive approach was developed to predict traffic and other land use related pollutants in urban stormwater based on traffic and other land use characteristics. This approach primarily included the development of a set of mathematical equations to predict traffic generated pollutants by linking traffic and land use characteristics to stormwater quality through mathematical modelling. The outcomes of this research will contribute to the design of appropriate treatment systems to safeguard urban receiving water quality for future traffic growth scenarios. The „real world. application of knowledge generated was demonstrated through mathematical modelling of solids in urban stormwater, accounting for the variability in traffic and land use characteristics.

Fixed bed pyrolysis of date seed waste for liquid oil production

The conversion of biomass waste in the form of date seed into pyrolysis oil by fixed bed pyrolysis reactor has been taken into consideration in this study. A fixed bed pyrolysis has been designed and fabricated for obtaining liquid fuel from these date seeds. The major component of the system are fixed bed pyrolysis reactor, liquid condenser and liquid collector. The date seed in particle form is pyrolysed in an externally heated 7.6 cm diameter and 46 cm high fixed bed reactor with nitrogen as the carrier gas. The reactor is heated by means of a biomass source cylindrical heater from 4000C to 6000C. The products are oil, char and gas. The reactor bed temperature, running time and feed particle size are considered as process parameters. The parameters are found to influence the product yield significantly. A maximum liquid yield of 50 wt.% is obtained at a reactor bed temperature of 5000 C for a feed size volume of 0.11- 0.20 cm3 with a running time of 120 minutes. The pyrolysis oil obtained at this optimum process conditions are analyzed for some fuel properties and compared with some other biomass derived pyrolysis oils and also with conventional fuels. The oil is found to possess favorable flash point and reasonable density and viscosity. The higher calorific value is found to be 28.636 MJ/kg which is significantly higher than other biomass derived pyrolysis oils.

Studies on the surface properties of biodegradable polymer carriers in respiratory delivery of drug from Dry Powder Inhaler formulations

Dry Powder Inhaler (DPI) technology has a significant impact in the treatment of various respiratory disorders. DPI formulations consist of a micronized drug (<5ìm) blended with an inert coarse carrier, for which lactose is widely used to date. DPIs are one of the inhalation devices which are used to target the delivery of drugs to the lungs. Drug delivery via DPI formulations is influenced by the physico-chemical characteristics of lactose particles such as size, shape, surface roughness and adhesional forces. Commercially available DPI formulations, which utilise lactose as the carrier, are not efficient in delivering drug to the lungs. The reasons for this are the surface morphology, adhesional properties and surface roughness of lactose. Despite several attempts to modify lactose, the maximum efficient drug delivery to the lungs remains limited; hence, exploring suitable alternative carriers for DPIs is of paramount importance. Therefore, the objective of the project was to study the performance of spherical polymer microparticles as drug carriers and the factors controlling their performance. This study aimed to use biodegradable polymer microspheres as alternative carriers to lactose in DPIs for achieving efficient drug delivery into the lungs. This project focused on fabricating biodegradable polymer microparticles with reproducible surface morphology and particle shape. The surface characteristics of polymeric carriers and the adhesional forces between the drug and carrier particles were investigated in order to gain a better understanding of their influence on drug dispersion. For this purpose, two biodegradable polymers- polycaprolactone (PCL) and poly (DL-lactide-co-glycolide) (PLGA) were used as the carriers to deliver the anti-asthmatic drug - Salbutamol Sulphate (SS). The first study conducted for this dissertation was the aerosolization of SS from mixtures of SS and PCL or PLGA microparticles. The microparticles were fabricated using an emulsion technique and were characterized by laser diffraction for particle size analysis, Scanning Electron Microscopy (SEM) for surface morphology and X-ray Photoelectron Spectroscopy (XPS) to obtain surface elemental composition. The dispersion of the drug from the DPI formulations was determined by using a Twin Stage Impinger (TSI). The Fine particle Fraction (FPF) of SS from powder mixtures was analyzed by High Performance Liquid Chromatography (HPLC). It was found that the drug did not detach from the surface of PCL microspheres. To overcome this, the microspheres were coated with anti-adherent agents such as magnesium stearate and leucine to improve the dispersion of the drug from the carrier surfaces. It was found that coating the PCL microspheres helped in significantly improving the FPF of SS from the PCL surface. These results were in contrast to the PLGA microspheres which readily allowed detachment of the SS from their surface. However, coating PLGA microspheres with antiadherent agents did not further improve the detachment of the drug from the surface. Thus, the first part of the study demonstrated that the surface-coated PCL microspheres and PLGA microspheres can be potential alternatives to lactose as carriers in DPI formulations; however, there was no significant improvement in the FPF of the drug. The second part of the research studied the influence of the size of the microspheres on the FPF of the drug. For this purpose, four different sizes (25 ìm, 48 ìm, 100 ìm and 150 ìm) of the PCL and PLGA microspheres were fabricated and characterized. The dispersion of the drug from microspheres of different sizes was determined. It was found that as the size of the carrier increased there was a significant increase in the FPF of SS. This study suggested that the size of the carrier plays an important role in the dispersion of the drug from the carrier surface. Subsequent experiments in the third part of the dissertation studied the surface properties of the polymeric carrier. The adhesion forces existing between the drug particle and the polymer surfaces, and the surface roughness of the carriers were quantified using Atomic Force Microscopy (AFM). A direct correlation between adhesion forces and dispersion of the drug from the carrier surface was observed suggesting that adhesion forces play an important role in determining the detachment potential of the drug from the carrier surface. However, no direct relationship between the surface roughness of the PCL or PLGA carrier and the FPF of the drug was observed. In conclusion, the body of work presented in this dissertation demonstrated the potential of coated PCL microspheres and PLGA microspheres to be used in DPI formulations as an alternative carrier to sugar based carriers. The study also emphasized the role of the size of the carrier particles and the forces of interaction prevailing between the drug and the carrier particle surface on the aerosolization performances of the drug.