976 resultados para Metals injection


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Atmospheric concentration of total suspended particulate matter (TSP) and associated heavy metals are a great concern due to their adverse health impacts and contribution to stormwater pollution. This paper discusses the outcomes of a study which investigated the variation of atmospheric TSP and heavy metal concentrations with traffic and land use characteristics during weekdays and weekends. Data for this study was gathered from fifteen sites at the Gold Coast, Australia using a high volume air sampler. The study detected consistently high TSP concentrations during weekdays compared to weekends. This confirms the significant influence of traffic related sources on TSP loads during weekdays. Both traffic and land use related sources equally contribute to TSP during weekends. Almost all the measured heavy metals showed high concentration on weekdays compared to weekends indicating significant contributions from traffic related emissions. Among the heavy metals, Zn concentration was the highest followed by Pb. It is postulated that re-suspension of previously deposited reserves was the main Pb source. Soil related sources were the main contributors of Mn.

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Traffic related emissions have been recognised as one of the main sources of air pollutants. In the research study discussed in this paper, variability of atmospheric total suspended particulate matter (TSP), polycyclic aromatic hydrocarbons (PAH) and heavy metal (HM) concentrations with traffic and land use characteristics during weekdays and weekends were investigated. Data required for the study were collected from a range of sampling sites to ensure a wide mix of traffic and land use characteristics. The analysis undertaken confirmed that zinc has the highest concentration in the atmospheric phase during weekends as well as weekdays. Although the use of leaded gasoline was discontinued a decade ago, lead was the second most commonly detected heavy metal. This is attributed to the association of previously generated lead with roadside soil and re-suspension to the atmosphere. Soil related particles are the primary source of TSP and manganese to the atmosphere. The analysis further revealed that traffic sources are dominant in gas phase PAHs compared to the other sources during weekdays. Land use related sources become important contributors to atmospheric PAHs during weekends when traffic sources are at their minimal levels.

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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.

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Alternative fuels and injection technologies are a necessary component of particulate emission reduction strategies for compression ignition engines. Consequently, this study undertakes a physicochemical characterization of diesel particulate matter (DPM) for engines equipped with alternative injection technologies (direct injection and common rail) and alternative fuels (ultra low sulfur diesel, a 20% biodiesel blend, and a synthetic diesel). Particle physical properties were addressed by measuring particle number size distributions, and particle chemical properties were addressed by measuring polycyclic aromatic hydrocarbons (PAHs) and reactive oxygen species (ROS). Particle volatility was determined by passing the polydisperse size distribution through a thermodenuder set to 300 °C. The results from this study, conducted over a four point test cycle, showed that both fuel type and injection technology have an impact on particle emissions, but injection technology was the more important factor. Significant particle number emission (54%–84%) reductions were achieved at half load operation (1% increase–43% decrease at full load) with the common rail injection system; however, the particles had a significantly higher PAH fraction (by a factor of 2 to 4) and ROS concentrations (by a factor of 6 to 16) both expressed on a test-cycle averaged basis. The results of this study have significant implications for the health effects of DPM emissions from both direct injection and common rail engines utilizing various alternative fuels.

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In the context of increasing demand for potable water and the depletion of water resources, stormwater is a logical alternative. However, stormwater contains pollutants, among which metals are of particular interest due to their toxicity and persistence in the environment. Hence, it is imperative to remove toxic metals in stormwater to the levels prescribed by drinking water guidelines for potable use. Consequently, various techniques have been proposed, among which sorption using low cost sorbents is economically viable and environmentally benign in comparison to other techniques. However, sorbents show affinity towards certain toxic metals, which results in poor removal of other toxic metals. It was hypothesised in this study that a mixture of sorbents that have different metal affinity patterns can be used for the efficient removal of a range of toxic metals commonly found in stormwater. The performance of six sorbents in the sorption of Al, Cr, Cu, Pb, Ni, Zn and Cd, which are the toxic metals commonly found in urban stormwater, was investigated to select suitable sorbents for creating the mixtures. For this purpose, a multi criteria analytical protocol was developed using the decision making methods: PROMETHEE (Preference Ranking Organisation METHod for Enrichment Evaluations) and GAIA (Graphical Analysis for Interactive Assistance). Zeolite and seaweed were selected for the creation of trial mixtures based on their metal affinity pattern and the performance on predetermined selection criteria. The metal sorption mechanisms employed by seaweed and zeolite were defined using kinetics, isotherm and thermodynamics parameters, which were determined using the batch sorption experiments. Additionally, the kinetics rate-limiting steps were identified using an innovative approach using GAIA and Spearman correlation techniques developed as part of the study, to overcome the limitation in conventional graphical methods in predicting the degree of contribution of each kinetics step in limiting the overall metal removal rate. The sorption kinetics of zeolite was found to be primarily limited by intraparticle diffusion followed by the sorption reaction steps, which were governed mainly by the hydrated ionic diameter of metals. The isotherm study indicated that the metal sorption mechanism of zeolite was primarily of a physical nature. The thermodynamics study confirmed that the energetically favourable nature of sorption increased in the order of Zn < Cu < Cd < Ni < Pb < Cr < Al, which is in agreement with metal sorption affinity of zeolite. Hence, sorption thermodynamics has an influence on the metal sorption affinity of zeolite. On the other hand, the primary kinetics rate-limiting step of seaweed was the sorption reaction process followed by intraparticle diffusion. The boundary layer diffusion was also found to limit the metal sorption kinetics at low concentration. According to the sorption isotherm study, Cd, Pb, Cr and Al were sorbed by seaweed via ion exchange, whilst sorption of Ni occurred via physisorption. Furthermore, ionic bonding is responsible for the sorption of Zn. The thermodynamics study confirmed that sorption by seaweed was energetically favourable in the order of Zn < Cu < Cd < Cr . Al < Pb < Ni. However, this did not agree with the affinity series derived for seaweed suggesting a limited influence of sorption thermodynamics on metal affinity for seaweed. The investigation of zeolite-seaweed mixtures indicated that mixing sorbents have an effect on the kinetics rates and the sorption affinity. Additionally, the theoretical relationships were derived to predict the boundary layer diffusion rate, intraparticle diffusion rate, the sorption reaction rate and the enthalpy of mixtures based on that of individual sorbents. In general, low coefficient of determination (R2) for the relationships between theoretical and experimental data indicated that the relationships were not statistically significant. This was attributed to the heterogeneity of the properties of sorbents. Nevertheless, in relative terms, the intraparticle diffusion rate, sorption reaction rate and enthalpy of sorption had higher R2 values than the boundary layer diffusion rate suggesting that there was some relationship between the former set of parameters of mixtures and that of sorbents. The mixture, which contained 80% of zeolite and 20% of seaweed, showed similar affinity for the sorption of Cu, Ni, Cd, Cr and Al, which was attributed to approximately similar sorption enthalpy of the metal ions. Therefore, it was concluded that the seaweed-zeolite mixture can be used to obtain the same affinity for various metals present in a multi metal system provided the metal ions have similar enthalpy during sorption by the mixture.

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The research study discussed in the paper investigated the adsorption/desorption behaviour of heavy metals commonly deposited on urban road surfaces, namely, Zn, Cu, Cr and Pb for different particle size ranges of solids. The study outcomes, based on field studies and batch experiments confirmed that road deposited solids particles contain a significantly high amount of vacant charge sites with the potential to adsorb additional heavy metals. Kinetic study and adsorption experiments indicated that Cr is the most preferred metal element to associate with solids due to the relatively high electro negativity and high charge density of trivalent cation (Cr3+). However, the relatively low availability of Cr in the urban road environment could influence this behaviour. Comparing total adsorbed metals present in solids particles, it was found that Zn has the highest capacity for adsorption to solids. Desorption experiments confirmed that a low concentration of Cu, Cr and Pb in solids was present in water-soluble and exchangeable form, whilst a significant fraction of adsorbed Zn has a high likelihood of being released back into solution. Among heavy metals, Zn is considered to be the most commonly available metal among road surface pollutants.

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Whilst the compression ignition (CI) engine exhibits many design advantages relative to its spark ignition engine counterpart; such as: high thermal efficiency, fuel economy and low carbon monoxide and hydrocarbon emissions, the issue of Diesel Particulate Matter (DPM) emissions continues to be an unresolved problem for the CI engine. Primarily, this thesis investigates a range of DPM mitigation strategies such as alternative fuels, injection technologies and combustion strategies conducted with a view to determine their impact on the physico-chemical properties of DPM emissions, and consequently to shed light on their likely human health impacts. Regulated gaseous emissions, Nitric oxide (NO), Carbon monoxide (CO), and Hydrocarbons (HCs), were measured in all experimental campaigns, although the major focus in this research program was on particulate emissions...

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Understanding the impacts of traffic and climate change on water quality helps decision makers to develop better policy and plans for dealing with unsustainable urban and transport development. This chapter presents detailed methodologies developed for sample collection and testing for heavy metals and total petroleum hydrocarbons, as part of a research study to investigate the impacts of climate change and changes to urban traffic characteristics on pollutant build-up and wash-off from urban road surfaces. Cadmium, chromium, nickel, copper, lead, iron, aluminium, manganese and zinc were the target heavy metals, and selected gasoline and diesel range organics were the target total petroleum hydrocarbons for this study. The study sites were selected to encompass the urban traffic characteristics of the Gold Coast region, Australia. An improved sample collection method referred to as ‘the wet and dry vacuum system’ for the pollutant build-up, and an effective wash-off plan to incorporate predicted changes to rainfall characteristics due to climate change, were implemented. The novel approach to sample collection for pollutant build-up helped to maintain the integrity of collection efficiency. The wash-off plan helped to incorporate the predicted impacts of climate change in the Gold Coast region. The robust experimental methods developed will help in field sample collection and chemical testing of different stormwater pollutants in build-up and wash-off.

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This paper presents a model for generating a MAC tag with a stream cipher using the input message indirectly. Several recent proposals represent instances of this model with slightly different options. We investigate the security of this model for different options, and identify cases which permit forgery attacks. Based on this, we present a new forgery attack on version 1.4 of 128-EIA3. Design recommendations to enhance the security of proposals following this general model are given.

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This paper presents a model for generating a MAC tag by injecting the input message directly into the internal state of a nonlinear filter generator. This model generalises a similar model for unkeyed hash functions proposed by Nakano et al. We develop a matrix representation for the accumulation phase of our model and use it to analyse the security of the model against man-in-the-middle forgery attacks based on collisions in the final register contents. The results of this analysis show that some conclusions of Nakano et al regarding the security of their model are incorrect. We also use our results to comment on several recent MAC proposals which can be considered as instances of our model and specify choices of options within the model which should prevent the type of forgery discussed here. In particular, suitable initialisation of the register and active use of a secure nonlinear filter will prevent an attacker from finding a collision in the final register contents which could result in a forged MAC.

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Stormwater is a potential and readily available alternative source for potable water in urban areas. However, its direct use is severely constrained by the presence of toxic pollutants, such as heavy metals (HMs). The presence of HMs in stormwater is of concern because of their chronic toxicity and persistent nature. In addition to human health impacts, metals can contribute to adverse ecosystem health impact on receiving waters. Therefore, the ability to predict the levels of HMs in stormwater is crucial for monitoring stormwater quality and for the design of effective treatment systems. Unfortunately, the current laboratory methods for determining HM concentrations are resource intensive and time consuming. In this paper, applications of multivariate data analysis techniques are presented to identify potential surrogate parameters which can be used to determine HM concentrations in stormwater. Accordingly, partial least squares was applied to identify a suite of physicochemical parameters which can serve as indicators of HMs. Datasets having varied characteristics, such as land use and particle size distribution of solids, were analyzed to validate the efficacy of the influencing parameters. Iron, manganese, total organic carbon, and inorganic carbon were identified as the predominant parameters that correlate with the HM concentrations. The practical extension of the study outcomes to urban stormwater management is also discussed.

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Atmospheric deposition is one of the most important pathways of urban stormwater pollution. Atmospheric deposition which can be in the form of either wet or dry deposition have distinct characteristics in terms of associated particulate sizes, pollutant types and influential parameters. This paper discusses the outcomes of a comprehensive research study undertaken to identify important traffic characteristics and climate factors such as antecedent dry period and rainfall characteristics which influences the characteristics of wet and dry deposition of solids and heavy metals. The outcomes confirmed that Zinc (Zn) is correlated with traffic volume whereas Lead (Pb), Cadmium (Cd), Nickel (Ni), and Copper (Cu) are correlated with traffic congestion. Consequently, reducing traffic congestion will be more effective than reducing traffic volume for improving air quality particularly in relation to Pb, Cd, Ni, and Cu. Zn was found to have the highest atmospheric deposition rate compared to other heavy metals. Zn in dry deposition is associated with relatively larger particle size fractions (>10 µm), whereas Pb, Cd, Ni and Cu are associated with relatively smaller particle size fractions (<10 µm). The analysis further revealed that bulk (wet plus dry) deposition which is correlated with rainfall depth and contains a relatively higher percentage of smaller particles compared to dry deposition which is correlated with the antecedent dry period. As particles subjected to wet deposition are smaller, they disperse over a larger area from the source of origin compared to particles subjected to dry deposition as buoyancy forces become dominant for smaller particles compared to the influence of gravity. Furthermore, exhaust emission particles were found to be primarily associated with bulk deposition compared to dry deposition particles which mainly originate from vehicle component wear.

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Knowledge of the elements present in house dusts is important in understanding potential health effects on humans. In this study, dust samples collected from 10 houses in south-east Queensland have been analysed by scanning electron microscopy and X-ray microanalysis to measure the inorganic element compositions and to investigate the form of heavy metals in the dusts. The overall analytical results were then used to discriminate between different localities using chemometric techniques. The relative amounts of elements, particularly of Si, Ca, and Fe, varied between size fractions and between different locations for the same size fraction. By analysing individual small particles, many other constituents were identified including Ti, Cr, Mn, Ni, Cu, Zn, Ba, Ag, W, Au, Hg, Pb, Bi, La and Ce. The heavy metals were mostly concentrated in small particles in the smaller size fractions, which allowed detection by particle analysis, though their average concentrations were very low.

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The research study discussed in the paper investigated the adsorption/desorption behaviour of heavy metals commonly deposited on urban road surfaces, namely, Zn, Cu, Cr and Pb for different particle size ranges of solids. The study outcomes, based on field studies and batch experiments confirmed that road deposited solids particles contain a significantly high amount of vacant charge sites with the potential to adsorb additional heavy metals. Kinetic studies and adsorption experiments indicated that Cr is the most preferred metal element to associate with solids due to the relatively high electro negativity and high charge density of trivalent cation (Cr3+). However, the relatively low availability of Cr in the urban road environment could influence this behaviour. Comparing total adsorbed metals present in solids particles, it was found that Zn has the highest capacity for adsorption to solids. Desorption experiments confirmed that a low concentration of Cu, Cr and Pb in solids was present in water-soluble and exchangeable form, whilst a significant fraction of adsorbed Zn has a high likelihood of being released back into solution. Among heavy metals, Zn is considered to be the most commonly available metal among road surface pollutants.