An investigation of gaseous and particulate emissions from compression ignition engines operated with alternative fuels, injection technologies, and combustion strategies

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...

Multi-criteria ranking and source apportionment of airborne particulate matter

Particulate matter research is essential because of the well known significant adverse effects of aerosol particles on human health and the environment. In particular, identification of the origin or sources of particulate matter emissions is of paramount importance in assisting efforts to control and reduce air pollution in the atmosphere. This thesis aims to: identify the sources of particulate matter; compare pollution conditions at urban, rural and roadside receptor sites; combine information about the sources with meteorological conditions at the sites to locate the emission sources; compare sources based on particle size or mass; and ultimately, provide the basis for control and reduction in particulate matter concentrations in the atmosphere. To achieve these objectives, data was obtained from assorted local and international receptor sites over long sampling periods. The samples were analysed using Ion Beam Analysis and Scanning Mobility Particle Sizer methods to measure the particle mass with chemical composition and the particle size distribution, respectively. Advanced data analysis techniques were employed to derive information from large, complex data sets. Multi-Criteria Decision Making (MCDM), a ranking method, drew on data variability to examine the overall trends, and provided the rank ordering of the sites and years that sampling was conducted. Coupled with the receptor model Positive Matrix Factorisation (PMF), the pollution emission sources were identified and meaningful information pertinent to the prioritisation of control and reduction strategies was obtained. This thesis is presented in the thesis by publication format. It includes four refereed papers which together demonstrate a novel combination of data analysis techniques that enabled particulate matter sources to be identified and sampling site/year ranked. The strength of this source identification process was corroborated when the analysis procedure was expanded to encompass multiple receptor sites. Initially applied to identify the contributing sources at roadside and suburban sites in Brisbane, the technique was subsequently applied to three receptor sites (roadside, urban and rural) located in Hong Kong. The comparable results from these international and national sites over several sampling periods indicated similarities in source contributions between receptor site-types, irrespective of global location and suggested the need to apply these methods to air pollution investigations worldwide. Furthermore, an investigation into particle size distribution data was conducted to deduce the sources of aerosol emissions based on particle size and elemental composition. Considering the adverse effects on human health caused by small-sized particles, knowledge of particle size distribution and their elemental composition provides a different perspective on the pollution problem. This thesis clearly illustrates that the application of an innovative combination of advanced data interpretation methods to identify particulate matter sources and rank sampling sites/years provides the basis for the prioritisation of future air pollution control measures. Moreover, this study contributes significantly to knowledge based on chemical composition of airborne particulate matter in Brisbane, Australia and on the identity and plausible locations of the contributing sources. Such novel source apportionment and ranking procedures are ultimately applicable to environmental investigations worldwide.

Effect of pulsed power on particle matter in diesel engine exhaust using a DBD plasma reactor

Nonthermal plasma (NTP) treatment of exhaust gas is a promising technology for both nitrogen oxides (NOX) and particulate matter (PM) reduction by introducing plasma into the exhaust gases. This paper considers the effect of NTP on PM mass reduction, PM size distribution, and PM removal efficiency. The experiments are performed on real exhaust gases from a diesel engine. The NTP is generated by applying high-voltage pulses using a pulsed power supply across a dielectric barrier discharge (DBD) reactor. The effects of the applied high-voltage pulses up to 19.44 kVpp with repetition rate of 10 kHz are investigated. In this paper, it is shown that the PM removal and PM size distribution need to be considered both together, as it is possible to achieve high PM removal efficiency with undesirable increase in the number of small particles. Regarding these two important factors, in this paper, 17 kVpp voltage level is determined to be an optimum point for the given configuration. Moreover, particles deposition on the surface of the DBD reactor is found to be a significant phenomenon, which should be considered in all plasma PM removal tests.

Source apportionment of airborne particulate matter : an overview of Australian and New Zealand studies

Despite the existence of air quality guidelines in Australia and New Zealand, the concentrations of particulate matter have exceeded these guidelines on several occasions. To identify the sources of particulate matter, examine the contributions of the sources to the air quality at specific areas and estimate the most likely locations of the sources, a growing number of source apportionment studies have been conducted. This paper provides an overview of the locations of the studies, salient features of the results obtained and offers some perspectives for the improvement of future receptor modelling of air quality in these countries. The review revealed that because of its advantages over alternative models, Positive Matrix Factorisation (PMF) was the most commonly applied model in the studies. Although there were differences in the sources identified in the studies, some general trends were observed. While biomass burning was a common problem in both countries, the characteristics of this source varied from one location to another. In New Zealand, domestic heating was the highest contributor to particle levels on days when the guidelines were exceeded. On the other hand, forest back-burning was a concern in Brisbane while marine aerosol was a major source in most studies. Secondary sulphate, traffic emissions, industrial emissions and re-suspended soil were also identified as important sources. Some unique species, for example, volatile organic compounds and particle size distribution were incorporated into some of the studies with results that have significant ramifications for the improvement of air quality. Overall, the application of source apportionment models provided useful information that can assist the design of epidemiological studies and refine air pollution reduction strategies in Australia and New Zealand.

To sonicate or not to sonicate PM filters: Reactive Oxygen Species generation upon ultrasonic irradiation

In aerosol research, a common approach for the collection of particulate matter (PM) is the use of filters in order to obtain sufficient material to undertake analysis. For subsequent chemical and toxicological analyses, in most of cases the PM needs to be extracted from the filters. Sonication is commonly used to most efficiently extract the PM from the filters. Extraction protocols generally involve 10 - 60 min of sonication. The energy of ultrasonic waves causes the formation and collapse of cavitation bubbles in the solution. Inside the collapsing cavities the localised temperatures and pressures can reach extraordinary values. Although fleeting, such conditions can lead to pyrolysis of the molecules present inside the cavitation bubbles (gases dissolved in the liquid and solvent vapours), which results in the production of free radicals and the generation of new compounds formed by reactions with these free radicals. For example, simple sonication of pure water will result in the formation of detectable levels of hydroxyl radicals. As hydroxyl radicals are recognised as playing key roles as oxidants in the atmosphere the extraction of PM from filters using sonication is therefore problematic. Sonication can result in significant chemical and physical changes to PM through thermal degradation and other reactions. In this article, an overview of sonication technique as used in aerosol research is provided, the capacity for radical generation under these conditions is described and an analysis is given of the impact of sonication-derived free radicals on three molecular probes commonly used by researchers in this field to detect Reactive Oxygen Species in PM.

Effects of biodiesel chemical composition on the chemical and physical properties of the primary and secondary diesel particulate matter

This thesis improves our insight towards the effects of using biodiesels on the particulate matter emission of diesel engines and contributes to our understanding of their potential adverse health effects. The novelty of this project is the use of biodiesel fuel with controlled chemical composition that enables us to relate changes of physiochemical properties of particles to specific properties of the biodiesel. For the first time, the possibility of a correlation of the volatility and the Reactive Oxygen Species concentration of the particles is investigated versus the saturation, oxygen content and carbon chain length of the fuel.

Chemical and source characterisation of size-segregated urban air particulate matter

Recent epidemiological studies have shown a consistent association of the mass concentration of urban air thoracic (PM10) and fine (PM2.5) particles with mortality and morbidity among cardiorespiratory patients. However, the chemical characteristics of different particulate size ranges and the biological mechanisms responsible for these adverse health effects are not well known. The principal aims of this thesis were to validate a high volume cascade impactor (HVCI) for the collection of particulate matter for physicochemical and toxicological studies, and to make an in-depth chemical and source characterisation of samples collected during different pollution situations. The particulate samples were collected with the HVCI, virtual impactors and a Berner low pressure impactor in six European cities: Helsinki, Duisburg, Prague, Amsterdam, Barcelona and Athens. The samples were analysed for particle mass, common ions, total and water-soluble elements as well as elemental and organic carbon. Laboratory calibration and field comparisons indicated that the HVCI can provide a unique large capacity, high efficiency sampling of size-segregated aerosol particles. The cutoff sizes of the recommended HVCI configuration were 2.4, 0.9 and 0.2 μm. The HVCI mass concentrations were in a good agreement with the reference methods, but the chemical composition of especially the fine particulate samples showed some differences. This implies that the chemical characterization of the exposure variable in toxicological studies needs to be done from the same HVCI samples as used in cell and animal studies. The data from parallel, low volume reference samplers provide valuable additional information for chemical mass closure and source assessment. The major components of PM2.5 in the virtual impactor samples were carbonaceous compounds, secondary inorganic ions and sea salt, whereas those of coarse particles (PM2.5-10) were soil-derived compounds, carbonaceous compounds, sea salt and nitrate. The major and minor components together accounted for 77-106% and 77-96% of the gravimetrically-measured masses of fine and coarse particles, respectively. Relatively large differences between sampling campaigns were observed in the organic carbon content of the PM2.5 samples as well as the mineral composition of the PM2.5-10 samples. A source assessment based on chemical tracers suggested clear differences in the dominant sources (e.g. traffic, residential heating with solid fuels, metal industry plants, regional or long-range transport) between the sampling campaigns. In summary, the field campaigns exhibited different profiles with regard to particulate sources, size distribution and chemical composition, thus, providing a highly useful setup for toxicological studies on the size-segregated HVCI samples.

Evaluation and modelling of the spatial and temporal variability of particulate matter in urban areas

This thesis contains three subject areas concerning particulate matter in urban area air quality: 1) Analysis of the measured concentrations of particulate matter mass concentrations in the Helsinki Metropolitan Area (HMA) in different locations in relation to traffic sources, and at different times of year and day. 2) The evolution of traffic exhaust originated particulate matter number concentrations and sizes in local street scale are studied by a combination of a dispersion model and an aerosol process model. 3) Some situations of high particulate matter concentrations are analysed with regard to their meteorological origins, especially temperature inversion situations, in the HMA and three other European cities. The prediction of the occurrence of meteorological conditions conducive to elevated particulate matter concentrations in the studied cities is examined. The performance of current numerical weather forecasting models in the case of air pollution episode situations is considered. The study of the ambient measurements revealed clear diurnal variation of the PM10 concentrations in the HMA measurement sites, irrespective of the year and the season of the year. The diurnal variation of local vehicular traffic flows seemed to have no substantial correlation with the PM2.5 concentrations, indicating that the PM10 concentrations were originated mainly from local vehicular traffic (direct emissions and suspension), while the PM2.5 concentrations were mostly of regionally and long-range transported origin. The modelling study of traffic exhaust dispersion and transformation showed that the number concentrations of particles originating from street traffic exhaust undergo a substantial change during the first tens of seconds after being emitted from the vehicle tailpipe. The dilution process was shown to dominate total number concentrations. Minimal effect of both condensation and coagulation was seen in the Aitken mode number concentrations. The included air pollution episodes were chosen on the basis of occurrence in either winter or spring, and having at least partly local origin. In the HMA, air pollution episodes were shown to be linked to predominantly stable atmospheric conditions with high atmospheric pressure and low wind speeds in conjunction with relatively low ambient temperatures. For the other European cities studied, the best meteorological predictors for the elevated concentrations of PM10 were shown to be temporal (hourly) evolutions of temperature inversions, stable atmospheric stability and in some cases, wind speed. Concerning the weather prediction during particulate matter related air pollution episodes, the use of the studied models were found to overpredict pollutant dispersion, leading to underprediction of pollutant concentration levels.

Simultaneous reduction of particulate matter and NOx emissions using 4-way catalyzed filtration systems

The next generation of diesel emission control devices includes 4-way catalyzed filtration systems (4WCFS) consisting of both NOx and diesel particulate matter (DPM) control. A methodology was developed to simultaneously evaluate the NOx and DPM control performance of miniature 4WCFS made from acicular mullite, an advanced ceramic material (ACM), that were challenged with diesel exhaust. The impact of catalyst loading and substrate porosity on catalytic performance of the NOx trap was evaluated. Simultaneously with NOx measurements, the real-time solid particle filtration performance of catalyst-coated standard and high porosity filters was determined for steady-state and regenerative conditions. The use of high porosity ACM 4-way catalyzed filtration systems reduced NOx by 99% and solid and total particulate matter by 95% when averaged over 10 regeneration cycles. A "regeneration cycle" refers to an oxidizing ("lean") exhaust condition followed by a reducing ("rich") exhaust condition resulting in NOx storage and NOx reduction (i.e., trap "regeneration"), respectively. Standard porosity ACM 4-way catalyzed filtration systems reduced NOx by 60-75% and exhibited 99.9% filtration efficiency. The rich/lean cycling used to regenerate the filter had almost no impact on solid particle filtration efficiency but impacted NOx control. Cycling resulted in the formation of very low concentrations of semivolatile nucleation mode particles for some 4WCFS formulations. Overall, 4WCFS show promise for significantly reducing diesel emissions into the atmosphere in a single control device. © 2013 American Chemical Society.

Studies on the adsorption equilibrium and kinetics of pentachlorophenol on suspended particulate matter of Donghu Lake water

In this paper, the adsorption equilibrium and kinetic behaviors of pentachlorophenol (PCP) on suspended particulate matter (SPM) in Donghu Lake water were investigated. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and their constants were evaluated. The results indicated that the adsorption of PCP on Donghu Lake SPM followed the Freundlich isotherm. Furthermore, the first order Lagergren rate equation and the pseudo-second order rate equation were used to describe the kinetic behaviors of PCP adsorption on Donghu Lake SPM, the rate constants were determined, and the kinetic process of the adsorption of PCP on Donghu Lake SPM followed the second order kinetic model.