968 resultados para HYDROCARBONS
Resumo:
This work investigates the computer modelling of the photochemical formation of smog products such as ozone and aerosol, in a system containing toluene, NOx and water vapour. In particular, the problem of modelling this process in the Commonwealth Scientific and Industrial Research Organization (CSIRO) smog chambers, which utilize outdoor exposure, is addressed. The primary requirement for such modelling is a knowledge of the photolytic rate coefficients. Photolytic rate coefficients of species other than N02 are often related to JNo2 (rate coefficient for the photolysis ofN02) by a simple factor, but for outdoor chambers, this method is prone to error as the diurnal profiles may not be similar in shape. Three methods for the calculation of diurnal JNo2 are investigated. The most suitable method for incorporation into a general model, is found to be one which determines the photolytic rate coefficients for N02, as well as several other species, from actinic flux, absorption cross section and quantum yields. A computer model was developed, based on this method, to calculate in-chamber photolysis rate coefficients for the CSIRO smog chambers, in which ex-chamber rate coefficients are adjusted by accounting for variation in light intensity by transmittance through the Teflon walls, albedo from the chamber floor and radiation attenuation due to clouds. The photochemical formation of secondary aerosol is investigated in a series of toluene-NOx experiments, which were performed in the CSIRO smog chambers. Three stages of aerosol formation, in plots of total particulate volume versus time, are identified: a delay period in which no significant mass of aerosol is formed, a regime of rapid aerosol formation (regime 1) and a second regime of slowed aerosol formation (regime 2). Two models are presented which were developed from the experimental data. One model is empirically based on observations of discrete stages of aerosol formation and readily allows aerosol growth profiles to be calculated. The second model is based on an adaptation of published toluene photooxidation mechanisms and provides some chemical information about the oxidation products. Both models compare favorably against the experimental data. The gross effects of precursor concentrations (toluene, NOx and H20) and ambient conditions (temperature, photolysis rate) on the formation of secondary aerosol are also investigated, primarily using the mechanism model. An increase in [NOx]o results in increased delay time, rate of aerosol formation in regime 1 and volume of aerosol formed in regime 1. This is due to increased formation of dinitrocresol and furanone products. An increase in toluene results in a decrease in the delay time and an increase in the rate of aerosol formation in regime 1, due to enhanced reactivity from the toluene products, such as the radicals from the photolysis of benzaldehyde. Water vapor has very little effect on the formation of aerosol volume, except that rates are slightly increased due to more OH radicals from reaction with 0(1D) from ozone photolysis. Increased temperature results in increased volume of aerosol formed in regime 1 (increased dinitrocresol formation), while increased photolysis rate results in increased rate of aerosol formation in regime 1. Both the rate and volume of aerosol formed in regime 2 are increased by increased temperature or photolysis rate. Both models indicate that the yield of secondary particulates from hydrocarbons (mass concentration aerosol formed/mass concentration hydrocarbon precursor) is proportional to the ratio [NOx]0/[hydrocarbon]0
Resumo:
Hydrocarbon spills on roads are a major safety concern for the driving public and can have severe cost impacts both on pavement maintenance and to the economy through disruption to services. The time taken to clean-up spills and re-open roads in a safe driving condition is an issue of increasing concern given traffic levels on major urban arterials. Thus, the primary aim of the research was to develop a sorbent material that facilitates rapid clean-up of road spills. The methodology involved extensive research into a range of materials (organic, inorganic and synthetic sorbents), comprehensive testing in the laboratory, scale-up and field, and product design (i.e. concept to prototype). The study also applied chemometrics to provide consistent, comparative methods of sorbent evaluation and performance. In addition, sorbent materials at every stage were compared against a commercial benchmark. For the first time, the impact of diesel on asphalt pavement has been quantified and assessed in a systematic way. Contrary to conventional thinking and anecdotal observations, the study determined that the action of diesel on asphalt was quite rapid (i.e. hours rather than weeks or months). This significant finding demonstrates the need to minimise the impact of hydrocarbon spills and the potential application of the sorbent option. To better understand the adsorption phenomenon, surface characterisation techniques were applied to selected sorbent materials (i.e. sand, organo-clay and cotton fibre). Brunauer Emmett Teller (BET) and thermal analysis indicated that the main adsorption mechanism for the sorbents occurred on the external surface of the material in the diffusion region (sand and organo-clay) and/or capillaries (cotton fibre). Using environmental scanning electron microscopy (ESEM), it was observed that adsorption by the interfibre capillaries contributed to the high uptake of hydrocarbons by the cotton fibre. Understanding the adsorption mechanism for these sorbents provided some guidance and scientific basis for the selection of materials. The study determined that non-woven cotton mats were ideal sorbent materials for clean-up of hydrocarbon spills. The prototype sorbent was found to perform significantly better than the commercial benchmark, displaying the following key properties: • superior hydrocarbon pick-up from the road pavement; • high hydrocarbon retention capacity under an applied load; • adequate field skid resistance post treatment; • functional and easy to use in the field (e.g. routine handling, transportation, application and recovery); • relatively inexpensive to produce due to the use of raw cotton fibre and simple production process; • environmentally friendly (e.g. renewable materials, non-toxic to environment and operators, and biodegradable); and • rapid response time (e.g. two minutes total clean-up time compared with thirty minutes for reference sorbents). The major outcomes of the research project include: a) development of a specifically designed sorbent material suitable for cleaning up hydrocarbon spills on roads; b) submission of patent application (serial number AU2005905850) for the prototype product; and c) preparation of Commercialisation Strategy to advance the sorbent product to the next phase (i.e. R&D to product commercialisation).
Resumo:
The Mount Isa Basin is a new concept used to describe the area of Palaeo- to Mesoproterozoic rocks south of the Murphy Inlier and inappropriately described presently as the Mount Isa Inlier. The new basin concept presented in this thesis allows for the characterisation of basin-wide structural deformation, correlation of mineralisation with particular lithostratigraphic and seismic stratigraphic packages, and the recognition of areas with petroleum exploration potential. The northern depositional margin of the Mount Isa Basin is the metamorphic, intrusive and volcanic complex here referred to as the Murphy Inlier (not the "Murphy Tectonic Ridge"). The eastern, southern and western boundaries of the basin are obscured by younger basins (Carpentaria, Eromanga and Georgina Basins). The Murphy Inlier rocks comprise the seismic basement to the Mount Isa Basin sequence. Evidence for the continuity of the Mount Isa Basin with the McArthur Basin to the northwest and the Willyama Block (Basin) at Broken Hill to the south is presented. These areas combined with several other areas of similar age are believed to have comprised the Carpentarian Superbasin (new term). The application of seismic exploration within Authority to Prospect (ATP) 423P at the northern margin of the basin was critical to the recognition and definition of the Mount Isa Basin. The Mount Isa Basin is structurally analogous to the Palaeozoic Arkoma Basin of Illinois and Arkansas in southern USA but, as with all basins it contains unique characteristics, a function of its individual development history. The Mount Isa Basin evolved in a manner similar to many well described, Phanerozoic plate tectonic driven basins. A full Wilson Cycle is recognised and a plate tectonic model proposed. The northern Mount Isa Basin is defined as the Proterozoic basin area northwest of the Mount Gordon Fault. Deposition in the northern Mount Isa Basin began with a rift sequence of volcaniclastic sediments followed by a passive margin drift phase comprising mostly carbonate rocks. Following the rift and drift phases, major north-south compression produced east-west thrusting in the south of the basin inverting the older sequences. This compression produced an asymmetric epi- or intra-cratonic clastic dominated peripheral foreland basin provenanced in the south and thinning markedly to a stable platform area (the Murphy Inlier) in the north. The fmal major deformation comprised east-west compression producing north-south aligned faults that are particularly prominent at Mount Isa. Potential field studies of the northern Mount Isa Basin, principally using magnetic data (and to a lesser extent gravity data, satellite images and aerial photographs) exhibit remarkable correlation with the reflection seismic data. The potential field data contributed significantly to the unravelling of the northern Mount Isa Basin architecture and deformation. Structurally, the Mount Isa Basin consists of three distinct regions. From the north to the south they are the Bowthorn Block, the Riversleigh Fold Zone and the Cloncurry Orogen (new names). The Bowthom Block, which is located between the Elizabeth Creek Thrust Zone and the Murphy Inlier, consists of an asymmetric wedge of volcanic, carbonate and clastic rocks. It ranges from over 10 000 m stratigraphic thickness in the south to less than 2000 min the north. The Bowthorn Block is relatively undeformed: however, it contains a series of reverse faults trending east-west that are interpreted from seismic data to be down-to-the-north normal faults that have been reactivated as thrusts. The Riversleigh Fold Zone is a folded and faulted region south of the Bowthorn Block, comprising much of the area formerly referred to as the Lawn Hill Platform. The Cloncurry Orogen consists of the area and sequences equivalent to the former Mount Isa Orogen. The name Cloncurry Orogen clearly distinguishes this area from the wider concept of the Mount Isa Basin. The South Nicholson Group and its probable correlatives, the Pilpah Sandstone and Quamby Conglomerate, comprise a later phase of now largely eroded deposits within the Mount Isa Basin. The name South Nicholson Basin is now outmoded as this terminology only applied to the South Nicholson Group unlike the original broader definition in Brown et al. (1968). Cored slimhole stratigraphic and mineral wells drilled by Amoco, Esso, Elf Aquitaine and Carpentaria Exploration prior to 1986, penetrated much of the stratigraphy and intersected both minor oil and gas shows plus excellent potential source rocks. The raw data were reinterpreted and augmented with seismic stratigraphy and source rock data from resampled mineral and petroleum stratigraphic exploration wells for this study. Since 1986, Comalco Aluminium Limited, as operator of a joint venture with Monument Resources Australia Limited and Bridge Oil Limited, recorded approximately 1000 km of reflection seismic data within the basin and drilled one conventional stratigraphic petroleum well, Beamesbrook-1. This work was the first reflection seismic and first conventional petroleum test of the northern Mount Isa Basin. When incorporated into the newly developed foreland basin and maturity models, a grass roots petroleum exploration play was recognised and this led to the present thesis. The Mount Isa Basin was seen to contain excellent source rocks coupled with potential reservoirs and all of the other essential aspects of a conventional petroleum exploration play. This play, although high risk, was commensurate with the enormous and totally untested petroleum potential of the basin. The basin was assessed for hydrocarbons in 1992 with three conventional exploration wells, Desert Creek-1, Argyle Creek-1 and Egilabria-1. These wells also tested and confrrmed the proposed basin model. No commercially viable oil or gas was encountered although evidence of its former existence was found. In addition to the petroleum exploration, indeed as a consequence of it, the association of the extensive base metal and other mineralisation in the Mount Isa Basin with hydrocarbons could not be overlooked. A comprehensive analysis of the available data suggests a link between the migration and possible generation or destruction of hydrocarbons and metal bearing fluids. Consequently, base metal exploration based on hydrocarbon exploration concepts is probably. the most effective technique in such basins. The metal-hydrocarbon-sedimentary basin-plate tectonic association (analogous to Phanerozoic models) is a compelling outcome of this work on the Palaeo- to Mesoproterozoic Mount lsa Basin. Petroleum within the Bowthom Block was apparently destroyed by hot brines that produced many ore deposits elsewhere in the basin.
Resumo:
This overview focuses on the application of chemometrics techniques for the investigation of soils contaminated by polycyclic aromatic hydrocarbons (PAHs) and metals because these two important and very diverse groups of pollutants are ubiquitous in soils. The salient features of various studies carried out in the micro- and recreational environments of humans, are highlighted in the context of the various multivariate statistical techniques available across discipline boundaries that have been effectively used in soil studies. Particular attention is paid to techniques employed in the geosciences that may be effectively utilized for environmental soil studies; classical multivariate approaches that may be used in isolation or as complementary methods to these are also discussed. Chemometrics techniques widely applied in atmospheric studies for identifying sources of pollutants or for determining the importance of contaminant source contributions to a particular site, have seen little use in soil studies, but may be effectively employed in such investigations. Suitable programs are also available for suggesting mitigating measures in cases of soil contamination, and these are also considered. Specific techniques reviewed include pattern recognition techniques such as Principal Components Analysis (PCA), Fuzzy Clustering (FC) and Cluster Analysis (CA); geostatistical tools include variograms, Geographical Information Systems (GIS), contour mapping and kriging; source identification and contribution estimation methods reviewed include Positive Matrix Factorisation (PMF), and Principal Component Analysis on Absolute Principal Component Scores (PCA/APCS). Mitigating measures to limit or eliminate pollutant sources may be suggested through the use of ranking analysis and multi criteria decision making methods (MCDM). These methods are mainly represented in this review by studies employing the Preference Ranking Organisation Method for Enrichment Evaluation (PROMETHEE) and its associated graphic output, Geometrical Analysis for Interactive Aid (GAIA).
Resumo:
Particulate pollution has been widely recognised as an important risk factor to human health. In addition to increases in respiratory and cardiovascular morbidity associated with exposure to particulate matter (PM), WHO estimates that urban PM causes 0.8 million premature deaths globally and that 1.5 million people die prematurely from exposure to indoor smoke generated from the combustion of solid fuels. Despite the availability of a huge body of research, the underlying toxicological mechanisms by which particles induce adverse health effects are not yet entirely understood. Oxidative stress caused by generation of free radicals and related reactive oxygen species (ROS) at the sites of deposition has been proposed as a mechanism for many of the adverse health outcomes associated with exposure to PM. In addition to particle-induced generation of ROS in lung tissue cells, several recent studies have shown that particles may also contain ROS. As such, they present a direct cause of oxidative stress and related adverse health effects. Cellular responses to oxidative stress have been widely investigated using various cell exposure assays. However, for a rapid screening of the oxidative potential of PM, less time-consuming and less expensive, cell-free assays are needed. The main aim of this research project was to investigate the application of a novel profluorescent nitroxide probe, synthesised at QUT, as a rapid screening assay in assessing the oxidative potential of PM. Considering that this was the first time that a profluorescent nitroxide probe was applied in investigating the oxidative stress potential of PM, the proof of concept regarding the detection of PM–derived ROS by using such probes needed to be demonstrated and a sampling methodology needed to be developed. Sampling through an impinger containing profluorescent nitroxide solution was chosen as a means of particle collection as it allowed particles to react with the profluorescent nitroxide probe during sampling, avoiding in that way any possible chemical changes resulting from delays between the sampling and the analysis of the PM. Among several profluorescent nitroxide probes available at QUT, bis(phenylethynyl)anthracene-nitroxide (BPEAnit) was found to be the most suitable probe, mainly due to relatively long excitation and emission wavelengths (λex= 430 nm; λem= 485 and 513 nm). These wavelengths are long enough to avoid overlap with the background fluorescence coming from light absorbing compounds which may be present in PM (e.g. polycyclic aromatic hydrocarbons and their derivatives). Given that combustion, in general, is one of the major sources of ambient PM, this project aimed at getting an insight into the oxidative stress potential of combustion-generated PM, namely cigarette smoke, diesel exhaust and wood smoke PM. During the course of this research project, it was demonstrated that the BPEAnit probe based assay is sufficiently sensitive and robust enough to be applied as a rapid screening test for PM-derived ROS detection. Considering that for all three aerosol sources (i.e. cigarette smoke, diesel exhaust and wood smoke) the same assay was applied, the results presented in this thesis allow direct comparison of the oxidative potential measured for all three sources of PM. In summary, it was found that there was a substantial difference between the amounts of ROS per unit of PM mass (ROS concentration) for particles emitted by different combustion sources. For example, particles from cigarette smoke were found to have up to 80 times less ROS per unit of mass than particles produced during logwood combustion. For both diesel and wood combustion it has been demonstrated that the type of fuel significantly affects the oxidative potential of the particles emitted. Similarly, the operating conditions of the combustion source were also found to affect the oxidative potential of particulate emissions. Moreover, this project has demonstrated a strong link between semivolatile (i.e. organic) species and ROS and therefore, clearly highlights the importance of semivolatile species in particle-induced toxicity.
Resumo:
Films found on the windows of residential buildings have been studied. The main aim of the paper was to assess the roles of the films in the accumulation of potentially toxic chemicals in residential buildings. Thus the elemental and polycyclic aromatic hydrocarbon compositions of the surface films from the glass windows of eighteen residential buildings were examined. The presence of sample amounts of inorganic elements (4.0–1.2 × 106 μg m−2) and polycyclic aromatic hydrocarbons in the films (BDL - 620.1 ng m−2) has implications for human exposure and the fate of pollutants in the urban environment. To facilitate the interpretation of the results, data matrices consisting of the chemical composition of the films and the building characteristics were subjected to multivariate data analysis methods, and these revealed that the accumulation of the chemicals was strongly dependent on building characteristics such as the type of glass used for the window, the distance from a major road, age of the building, distance from an industrial activity, number of smokers in the building and frequency of cooking in the buildings. Thus, building characteristics which minimize the accumulation of pollutants on the surface films need to be encouraged.
Resumo:
The emissions to water from a 1.9 kW two-stroke outboard engine were investigated in the laboratory and in the field, with the primary objective being to characterise and quantify the pollutants that remain within the water column. The emission rates of polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs) were determined for the engine when using a mineral and an equivalent environmentally adapted lubricant (EAL). A comparison of the emission rates was conducted between the results from the fresh and sea water tests. The results showed that there was little difference in the emission rates of these pollutants when either of the lubricants was used in both the fresh and sea water. A further set of tests were done to find out the effect on pH of water due to the underwater emissions and these tests were done using both mineral and environmentally adapted lubricant. The results showed that the type of lubricant does not have any effect on the change in pH of the water.
Resumo:
Urban traffic and climate change are two phenomena that have the potential to degrade urban water quality by influencing the build-up and wash-off of pollutants, respectively. However, limited knowledge has made it difficult to establish any link between pollutant buildup and wash-off under such dynamic conditions. In order to safeguard urban water quality, adaptive water quality mitigation measures are required. In this research, pollutant build-up and wash-off have been investigated from a dynamic point of view which incorporated the impacts of changed urban traffic as well as changes in the rainfall characteristics induced by climate change. The study has developed a dynamic object classification system and thereby, conceptualised the study of pollutant build-up and wash-off under future changes in urban traffic and rainfall characteristics. This study has also characterised the buildup and wash-off processes of traffic generated heavy metals, volatile, semi-volatile and non-volatile hydrocarbons under dynamic conditions which enables the development of adaptive mitigation measures for water quality. Additionally, predictive frameworks for the build-up and wash-off of some pollutants have also been developed.
Resumo:
This study undertook a physico-chemical characterisation of particle emissions from a single compression ignition engine operated at one test mode with 3 biodiesel fuels made from 3 different feedstocks (i.e. soy, tallow and canola) at 4 different blend percentages (20%, 40%, 60% and 80%) to gain insights into their particle-related health effects. Particle physical properties were inferred by measuring particle number size distributions both with and without heating within a thermodenuder (TD) and also by measuring particulate matter (PM) emission factors with an aerodynamic diameter less than 10 μm (PM10). The chemical properties of particulates were investigated by measuring particle and vapour phase Polycyclic Aromatic Hydrocarbons (PAHs) and also Reactive Oxygen Species (ROS) concentrations. The particle number size distributions showed strong dependency on feedstock and blend percentage with some fuel types showing increased particle number emissions, whilst others showed particle number reductions. In addition, the median particle diameter decreased as the blend percentage was increased. Particle and vapour phase PAHs were generally reduced with biodiesel, with the results being relatively independent of the blend percentage. The ROS concentrations increased monotonically with biodiesel blend percentage, but did not exhibit strong feedstock variability. Furthermore, the ROS concentrations correlated quite well with the organic volume percentage of particles – a quantity which increased with increasing blend percentage. At higher blend percentages, the particle surface area was significantly reduced, but the particles were internally mixed with a greater organic volume percentage (containing ROS) which has implications for using surface area as a regulatory metric for diesel particulate matter (DPM) emissions.
Resumo:
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.
Resumo:
A 4-cylinder Ford 2701C test engine was used in this study to explore the impact of ethanol fumigation on gaseous and particle emission concentrations. The fumigation technique delivered vaporised ethanol into the intake manifold of the engine, using an injector, a pump and pressure regulator, a heat exchanger for vaporising ethanol and a separate fuel tank and lines. Gaseous (Nitric oxide (NO), Carbon monoxide (CO) and hydrocarbons (HC)) and particulate emissions (particle mass (PM2.5) and particle number) testing was conducted at intermediate speed (1700 rpm) using 4 load settings with ethanol substitution percentages ranging from 10-40 % (by energy). With ethanol fumigation, NO and PM2.5 emissions were reduced, whereas CO and HC emissions increased considerably and particle number emissions increased at most test settings. It was found that ethanol fumigation reduced the excess air factor for the engine and this led to increased emissions of CO and HC, but decreased emissions of NO. PM2.5 emissions were reduced with ethanol fumigation, as ethanol has a very low “sooting” tendency. This is due to the higher hydrogen-to-carbon ratio of this fuel, and also because ethanol does not contain aromatics, both of which are known soot precursors. The use of a diesel oxidation catalyst (as an after-treatment device) is recommended to achieve a reduction in the four pollutants that are currently regulated for compression ignition engines. The increase in particle number emissions with ethanol fumigation was due to the formation of volatile (organic) particles; consequently, using a diesel oxidation catalyst will also assist in reducing particle number emissions.