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.

Particle emissions, volatility, and toxicity from an ethanol fumigated compression ignition engine

Particle emissions, volatility, and the concentration of reactive oxygen species (ROS) were investigated for a pre-Euro I compression ignition engine to study the potential health impacts of employing ethanol fumigation technology. Engine testing was performed in two separate experimental campaigns with most testing performed at intermediate speed with four different load settings and various ethanol substitutions. A scanning mobility particle sizer (SMPS) was used to determine particle size distributions, a volatilization tandem differential mobility analyzer (V-TDMA) was used to explore particle volatility, and a new profluorescent nitroxide probe, BPEAnit, was used to investigate the potential toxicity of particles. The greatest particulate mass reduction was achieved with ethanol fumigation at full load, which contributed to the formation of a nucleation mode. Ethanol fumigation increased the volatility of particles by coating the particles with organic material or by making extra organic material available as an external mixture. In addition, the particle-related ROS concentrations increased with ethanol fumigation and were associated with the formation of a nucleation mode. The smaller particles, the increased volatility, and the increase in potential particle toxicity with ethanol fumigation may provide a substantial barrier for the uptake of fumigation technology using ethanol as a supplementary fuel.

Characterization of acyl chain position in unsaturated phosphatidylcholines using differential mobility-mass spectrometry

Glycerophospholipids (GPs) that differ in the relative position of the two fatty acyl chains on the glycerol backbone (i.e., sn-positional isomers) can have distinct physicochemical properties. The unambiguous assignment of acyl chain position to an individual GP represents a significant analytical challenge. Here we describe a workflow where phosphatidylcholines (PCs) are subjected to ESI for characterization by a combination of differential mobility spectrometry and MS (DMS-MS). When infused as a mixture, ions formed from silver adduction of each phospholipid isomer {e.g., [PC (16:0/18:1) + Ag]+ and [PC (18:1/16:0) + Ag]+} are transmitted through the DMS device at discrete compensation voltages. Varying their relative amounts allows facile and unambiguous assignment of the sn-positions of the fatty acyl chains for each isomer. Integration of the well-resolved ion populations provides a rapid method (< 3 min) for relative quantification of these lipid isomers. The DMS-MS results show excellent agreement with established, but time-consuming, enzymatic approaches and also provide superior accuracy to methods that rely on MS alone. The advantages of this DMS-MS method in identification and quantification of GP isomer populations is demonstrated by direct analysis of complex biological extracts without any prior fractionation.

A radial differential mobility analyzer for the size-classification of gas-phase synthesized nanoparticles at low pressures

Differential mobility analyzers (DMAs) are commonly used to generate monodisperse nanoparticle aerosols. Commercial DMAs operate at quasi-atmospheric pressures and are therefore not designed to be vacuum-tight. In certain particle synthesis methods, the use of a vacuum-compatible DMA is a requirement as a process step for producing high-purity metallic particles. A vacuum-tight radial DMA (RDMA) has been developed and tested at low pressures. Its performance has been evaluated by using a commercial NANO-DMA as the reference. The performance of this low-pressure RDMA (LP-RDMA) in terms of the width of its transfer function is found to be comparable with that of other NANO-DMAs at atmospheric pressure and is almost independent of the pressure down to 30 mbar. It is shown that LP-RDMA can be used for the classification of nanometer-sized particles (5-20 nm) under low pressure condition (30 mbar) and has been successfully applied to nanoparticles produced by ablating FeNi at low pressures.

New particle formation and growth at a remote, sub-tropical coastal location

A month-long intensive measurement campaign was conducted in March/April 2007 at Agnes Water, a remote coastal site just south of the Great Barrier Reef on the east coast of Australia. Particle and ion size distributions were continuously measured during the campaign. Coastal nucleation events were observed in clean, marine air masses coming from the south-east on 65% of the days. The events usually began at ~10:00 local time and lasted for 1-4 hrs. They were characterised by the appearance of a nucleation mode with a peak diameter of ~10 nm. The freshly nucleated particles grew within 1-4 hrs up to sizes of 20-50 nm. The events occurred when solar intensity was high (~1000 W m-2) and RH was low (~60%). Interestingly, the events were not related to tide height. The volatile and hygroscopic properties of freshly nucleated particles (17-22.5 nm), simultaneously measured with a volatility-hygroscopicity-tandem differential mobility analyser (VH-TDMA), were used to infer chemical composition. The majority of the volume of these particles was attributed to internally mixed sulphate and organic components. After ruling out coagulation as a source of significant particle growth, we conclude that the condensation of sulphate and/or organic vapours was most likely responsible for driving particle growth during the nucleation events. We cannot make any direct conclusions regarding the chemical species that participated in the initial particle nucleation. However, we suggest that nucleation may have resulted from the photo-oxidation products of unknown sulphur or organic vapours emitted from the waters of Hervey Bay, or from the formation of DMS-derived sulphate clusters over the open ocean that were activated to observable particles by condensable vapours emitted from the nutrient rich waters around Fraser Island or Hervey Bay. Furthermore, a unique and particularly strong nucleation event was observed during northerly wind. The event began early one morning (08:00) and lasted almost the entire day resulting in the production of a large number of ~80 nm particles (average modal concentration during the event was 3200 cm-3). The Great Barrier Reef was the most likely source of precursor vapours responsible for this event.

Water uptake of aerosols with a focus on seeded aerosols and instrumentation techniques

This thesis focuses on the volatile and hygroscopic properties of mixed aerosol species. In particular, the influence organic species of varying solubility have upon seed aerosols. Aerosol studies were conducted at the Paul Scherrer Institut Laboratory for Atmospheric Chemistry (PSI-LAC, Villigen, Switzerland) and at the Queensland University of Technology International Laboratory for Air Quality and Health (QUT-ILAQH, Brisbane, Australia). The primary measurement tool employed in this program was the Volatilisation and Hygroscopicity Tandem Differential Mobility Analyser (VHTDMA - Johnson et al. 2004). This system was initially developed at QUT within the ILAQH and was completely re-developed as part of this project (see Section 1.4 for a description of this process). The new VHTDMA was deployed to the PSI-LAC where an analysis of the volatile and hygroscopic properties of ammonium sulphate seeds coated with organic species formed from the photo-oxidation of á-pinene was conducted. This investigation was driven by a desire to understand the influence of atmospherically prevalent organics upon water uptake by material with cloud forming capabilities. Of particular note from this campaign were observed influences of partially soluble organic coatings upon inorganic ammonium sulphate seeds above and below their deliquescence relative humidity (DRH). Above the DRH of the seed increasing the volume fraction of the organic component was shown to reduce the water uptake of the mixed particle. Below the DRH the organic was shown to activate the water uptake of the seed. This was the first time this effect had been observed for á-pinene derived SOA. In contrast with the simulated aerosols generated at the PSI-LAC a case study of the volatile and hygroscopic properties of diesel emissions was undertaken. During this stage of the project ternary nucleation was shown, for the first time, to be one of the processes involved in formation of diesel particulate matter. Furthermore, these particles were shown to be coated with a volatile hydrophobic material which prevented the water uptake of the highly hygroscopic material below. This result was a first and indicated that previous studies into the hygroscopicity of diesel emission had erroneously reported the particles to be hydrophobic. Both of these results contradict the previously upheld Zdanovksii-Stokes-Robinson (ZSR) additive rule for water uptake by mixed species. This is an important contribution as it adds to the weight of evidence that limits the validity of this rule.

Intercomparison study of six HTDMAs: results and recommendations

We report on an inter-comparison of six different hygroscopicity tandem differential mobility analysers (HTDMAs). These HTDMAs are used worldwide in laboratories and in field campaigns to measure the water uptake of aerosol particles and were never intercompared. After an investigation of the different design of the instruments with their advantages and inconveniencies, the methods for calibration, validation and analysis are presented. Measurements of nebulised ammonium sulphate as well as of secondary organic aerosol generated from a smog chamber were performed. Agreement and discrepancies between the instrument and to the theory are discussed, and final recommendations for a standard instrument are given, as a benchmark for laboratory or field experiments to ensure a high quality of HTDMA data.

The organic fraction of bubble-generated, accumulation mode Sea Spray Aerosol (SSA)

Recent studies have detected a dominant accumulation mode (~100 nm) in the Sea Spray Aerosol (SSA) number distribution. There is evidence to suggest that particles in this mode are composed primarily of organics. To investigate this hypothesis we conducted experiments on NaCl, artificial SSA and natural SSA particles with a Volatility-Hygroscopicity-Tandem-Differential-Mobility-Analyser (VH-TDMA). NaCl particles were atomiser generated and a bubble generator was constructed to produce artificial and natural SSA particles. Natural seawater samples for use in the bubble generator were collected from biologically active, terrestrially-affected coastal water in Moreton Bay, Australia. Differences in the VH-TDMA-measured volatility curves of artificial and natural SSA particles were used to investigate and quantify the organic fraction of natural SSA particles. Hygroscopic Growth Factor (HGF) data, also obtained by the VH-TDMA, were used to confirm the conclusions drawn from the volatility data. Both datasets indicated that the organic fraction of our natural SSA particles evaporated in the VH-TDMA over the temperature range 170–200°C. The organic volume fraction for 71–77 nm natural SSA particles was 8±6%. Organic volume fraction did not vary significantly with varying water residence time (40 secs to 24 hrs) in the bubble generator or SSA particle diameter in the range 38–173 nm. At room temperature we measured shape- and Kelvin-corrected HGF at 90% RH of 2.46±0.02 for NaCl, 2.35±0.02 for artifical SSA and 2.26±0.02 for natural SSA particles. Overall, these results suggest that the natural accumulation mode SSA particles produced in these experiments contained only a minor organic fraction, which had little effect on hygroscopic growth. Our measurement of 8±6% is an order of magnitude below two previous measurements of the organic fraction in SSA particles of comparable sizes. We stress that our results were obtained using coastal seawater and they can’t necessarily be applied on a regional or global ocean scale. Nevertheless, considering the order of magnitude discrepancy between this and previous studies, further research with independent measurement techniques and a variety of different seawaters is required to better quantify how much organic material is present in accumulation mode SSA.

Widening the gap between measurement and modelling of secondary organic aerosol properties?

The link between measured sub-saturated hygroscopicity and cloud activation potential of secondary organic aerosol particles produced by the chamber photo-oxidation of α-pinene in the presence or absence of ammonium sulphate seed aerosol was investigated using two models of varying complexity. A simple single hygroscopicity parameter model and a more complex model (incorporating surface effects) were used to assess the detail required to predict the cloud condensation nucleus (CCN) activity from the subsaturated water uptake. Sub-saturated water uptake measured by three hygroscopicity tandem differential mobility analyser (HTDMA) instruments was used to determine the water activity for use in the models. The predicted CCN activity was compared to the measured CCN activation potential using a continuous flow CCN counter. Reconciliation using the more complex model formulation with measured cloud activation could be achieved widely different assumed surface tension behavior of the growing droplet; this was entirely determined by the instrument used as the source of water activity data. This unreliable derivation of the water activity as a function of solute concentration from sub-saturated hygroscopicity data indicates a limitation in the use of such data in predicting cloud condensation nucleus behavior of particles with a significant organic fraction. Similarly, the ability of the simpler single parameter model to predict cloud activation behaviour was dependent on the instrument used to measure sub-saturated hygroscopicity and the relative humidity used to provide the model input. However, agreement was observed for inorganic salt solution particles, which were measured by all instruments in agreement with theory. The difference in HTDMA data from validated and extensively used instruments means that it cannot be stated with certainty the detail required to predict the CCN activity from sub-saturated hygroscopicity. In order to narrow the gap between measurements of hygroscopic growth and CCN activity the processes involved must be understood and the instrumentation extensively quality assured. It is impossible to say from the results presented here due to the differences in HTDMA data whether: i) Surface tension suppression occurs ii) Bulk to surface partitioning is important iii) The water activity coefficient changes significantly as a function of the solute concentration.

Observation of the suppression of water uptake by marine particles

A 4 week intensive measurement campaign was conducted in March–April 2007 at Agnes Water, a remote coastal site on the east coast of Australia. A Volatility-Hygroscopicity-Tandem Differential Mobility Analyser (VH-TDMA) was used to investigate changes in the hygroscopic properties of ambient particles as volatile components were progressively evaporated. Nine out of 18 VH-TDMA volatility scans detected internally mixed multi-component particles in the nucleation and Aitken modes in clean marine air. Evaporation of a volatile, organic-like component in the VH-TDMA caused significant increases in particle hygroscopicity. In 3 scans the increase in hygroscopicity was so large it was explained by an increase in the absolute volume of water uptake by the particle residuals, and not merely an increase in their relative hygroscopicity. This indicates 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). This observation was supported by ZSR calculations for one scan, which showed that the measured growth factors of mixed particles were up to 18% below those predicted assuming independent water uptake of the individual particle components. The observed suppression of water uptake could be due to a reduced rate of hygroscopic growth caused by the presence of organic films or organic-inorganic interactions in solution droplets that had a negative effect on hygroscopicity.

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.

Marine aerosol hygroscopicity and volatility, measured on the Chatham Rise (New Zealand)

The Surface Ocean Aerosol Production (SOAP) study was undertaken in February/March 2012 in the biologically active waters of the Chatham Rise, NZ. Aerosol hygroscopicity and volatility were examined with a volatility hygroscopicity tandem differential mobility analyser. These observations confirm results from other hygroscopicity-based studies that the dominant fraction of the observed remote marine particles were non-sea salt sulfates. Further observations are required to clarify the influences of seawater composition, meteorology and analysis techniques seasonally across different ocean basins.

Charged particles and cluster ions produced during cooking activities

Previous studies showed that a significant number of the particles present in indoor air are generated by cooking activities, and measured particle concentrations and exposures have been used to estimate the related human dose. The dose evaluation can be affected by the particle charge level which is usually not considered in particle deposition models. To this purpose, in this paper we show, for the very first time, the electric charge of particles generated during cooking activities and thus extending the interest on particle charging characterization to indoor micro-environments, so far essentially focused on outdoors. Particle number, together with positive and negative cluster ion concentrations, was monitored using a condensation particle counter and two air ion counters, respectively, during different cooking events. Positively-charged particle distribution fractions during gas combustion, bacon grilling, and eggplant grilling events were measured by two Scanning Mobility Particle Sizer spectrometers, used with and without a neutralizer. Finally, a Tandem Differential Mobility Analyzer was used to measure the charge specific particle distributions of bacon and eggplant grilling experiments, selecting particles of 30, 50, 80 and 100 nm in mobility diameter. The total fraction of positively-charged particles was 4.0%, 7.9%, and 5.6% for gas combustion, bacon grilling, and eggplant grilling events, respectively, then lower than other typical outdoor combustion-generated particles.