The formation of gold nanoparticles using hydroquinone as a reducing agent through a localized pH change upon addition of NaOH to a solution of HAuCl4

We demonstrate a rapid synthesis of gold nanoparticles using hydroquinone as a reducing agent under acidic conditions without the need for precursor seed particles. The nanoparticle formation process is facilitated by the addition of NaOH to a solution containing HAuCl4 and hydroquinone to locally change the pH; this enhances the reducing capability of hydroquinone to form gold nucleation centres, after which further growth of gold can take place through an autocatalytic mechanism. The stability of the nanoparticles is highly dependent on the initial solution pH, and both the concentration of added NaOH and hydroquinone present in solution. The gold nanoparticles were characterized by UV–visible spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, atomic force microscopy, dynamic light scattering, and zeta potential measurements. It was found that under optimal conditions that stable aqueous suspensions of 20 nm diameter nanoparticles can be achieved where benzoquinone, the oxidized product of hydroquinone, acts as a capping agent preventing nanoparticles aggregation.

Influence of biodiesel fuel composition on the morphology and microstructure of particles emitted from diesel engines

This study investigates the morphology, microstructure and surface composition of Diesel engine exhaust particles. The state of agglomeration, the primary particle size and the fractal dimension of exhaust particles from petroleum Diesel (petrodiesel) and biodiesel blends from microalgae, cotton seed and waste cooking oil were investigated by means of high resolution transmission electron microscopy. With primary particle diameters between 12-19 nm, biodiesel blend primary particles are found to be smaller than petrodiesel ones (21±2 nm). Also it was found that soot agglomerates from biodiesels are more compact and spherical, as their fractal dimensions are higher, e.g. 2.2±0.1 for 50% algae biodiesel compared to 1.7±0.1 for petrodiesel. In addition, analysis of the chemical composition by means of x-ray photoelectron spectroscopy revealed an up to a factor of two increased oxygen content on the primary particle surface for biodiesel. The length, curvature and distance of graphene layers were measured showing a greater structural disorder for biodiesel with shorter fringes of higher tortuosity. This change in carbon chemistry may reflect the higher oxygen content of biofuels. Overall, it seems that the oxygen content in the fuels is the underlying reason for the observed morphological change in the resulting soot particles.

Diesel bus emissions of submicrometer particles measured in a tunnel study

The emission factors of a bus fleet consisting of approximately three hundreds diesel powered buses were measured in a tunnel study under well controlled conditions during a two-day monitoring campaign in Brisbane. The number concentration of particles in the size range 0.017-0.7 m was monitored simultaneously by two Scanning Mobility Particle Sizers located at the tunnel’s entrance and exit. The mean value of the number emission factors was found to be (2.44±1.41)×1014 particles km-1. The results are in good agreement with the emission factors determined from steady-state dynamometer testing of 12 buses from the same Brisbane City bus fleet, thus indicating that when carefully designed, both approaches, the dynamometer and on-road studies, can provide comparable results, applicable for the assessment of the effect of traffic emissions on airborne particle pollution.

Indoor exposure to submicrometer particles and PM2.5 in residential houses in Brisbane, Australia

As part of a large study investigating indoor air in residential houses in Brisbane, Australia, the purpose of this work was to quantify indoor exposure to submicrometer particles and PM2.5 for the inhabitants of 14 houses. Particle concentrations were measured simultaneously for more than 48 hours in the kitchens of all the houses by using a condensation particle counter (CPC) and a photometer (DustTrak). The occupants of the houses were asked to fill in a diary, noting the time and duration of any activity occurring throughout the house during measurement, as well as their presence or absence from home. From the time series concentration data and the information about indoor activities, exposure to the inhabitants of the houses was calculated for the entire time they spent at home as well as during indoor activities resulting in particle generation. The results show that the highest median concentration level occurred during cooking periods for both particle number concentration (47.5´103 particles cm-3) and PM2.5 concentration (13.4 mg m-3). The highest residential exposure period was the sleeping period for both particle number exposure (31%) and PM2.5 exposure (45.6%). The percentage of the average residential particle exposure level in total 24h particle exposure level was approximating 70% for both particle number and PM2.5 exposure.

Relationship between indoor/outdoor concentrations of particles : a critical review

The relationship between indoor and outdoor concentration levels of particles in the absence and in the presence of indoor sources has been attracting an increasing level of attention. Understanding of the relationship and the mechanisms driving it, as well as the ability to quantify it, are of importance for assessment of source contribution, assessment of human exposure and for control and management of particles. It became particularly important to address this topic when evidence came from epidemiological studies on the close association between outdoor concentration levels of particles and health effects, yet with many studies showing that indoor concentrations could be significantly higher than those outdoors. This paper presents a summary of an extensive literature review on this topic conducted with an aim to identify general trends in relation to the I/O relationship emerging from studies conducted worldwide. The review considered separately a larger body of papers published on PM10, PM2.5, as well as the smaller database on particle number and number or volume size distribution. A specific focus of this paper is on naturally ventilated houses. The conclusion from the review is that despite the multiplicity of factors that play role in affecting the relationship, there are clear trends emerging in relation to the I/O relationship for particle mass concentration, enabling more general predictions to be made about the relationship. However, more research is still needed on particle number concentration and size distribution.

On the efficiency of impingers with fritted nozzle tip for collection of ultrafine particles

The aim of this study was to determine the collection efficiency of ultrafine particles into an impinger fitted with a fritted nozzle tip as a means to increase contact surface area between the aerosol and the liquid. The influence of liquid sampling volume, frit porosity and the nature of the sampling liquid was explored and it was shown that all impact on the collection efficiency of particles smaller than 220 nm. Obtained values for overall collection efficiency were substantially higher (~30–95%) than have been previously reported, mainly due to the high deposition of particles in the fritted nozzle tip, especially in case of finer porosity frits and smaller particles. Values for the capture efficiency of the solvent alone ranged from 20 to 45%, depending on the type and the volume of solvent. Additionally, our results show that airstream dispersion into bubbles improves particle trapping by the liquid and that there is a difference in collection efficiencies based on the nature and volume of the solvent used.

Error, Bias, and Long-Branch Attraction in Data for Two Chloroplast Photosystem Genes in Seed Plants

Sequences of two chloroplast photosystem genes, psaA and psbB, together comprising about 3,500 bp, were obtained for all five major groups of extant seed plants and several outgroups among other vascular plants. Strongly supported, but significantly conflicting, phylogenetic signals were obtained in parsimony analyses from partitions of the data into first and second codon positions versus third positions. In the former, both genes agreed on a monophyletic gymnosperms, with Gnetales closely related to certain conifers. In the latter, Gnetales are inferred to be the sister group of all other seed plants, with gymnosperms paraphyletic. None of the data supported the modern ‘‘anthophyte hypothesis,’’ which places Gnetales as the sister group of flowering plants. A series of simulation studies were undertaken to examine the error rate for parsimony inference. Three kinds of errors were examined: random error, systematic bias (both properties of finite data sets), and statistical inconsistency owing to long-branch attraction (an asymptotic property). Parsimony reconstructions were extremely biased for third-position data for psbB. Regardless of the true underlying tree, a tree in which Gnetales are sister to all other seed plants was likely to be reconstructed for these data. None of the combinations of genes or partitions permits the anthophyte tree to be reconstructed with high probability. Simulations of progressively larger data sets indicate the existence of long-branch attraction (statistical inconsistency) for third-position psbB data if either the anthophyte tree or the gymnosperm tree is correct. This is also true for the anthophyte tree using either psaA third positions or psbB first and second positions. A factor contributing to bias and inconsistency is extremely short branches at the base of the seed plant radiation, coupled with extremely high rates in Gnetales and nonseed plant outgroups. M. J. Sanderson,* M. F. Wojciechowski,*† J.-M. Hu,* T. Sher Khan,* and S. G. Brady

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.

Ultrafine particles in indoor air of a school : possible role of secondary organic aerosols

The aim of this work was to investigate ultrafine particles (< 0.1 μm) in primary school classrooms, in relation to the classrooms activities. The investigations were conducted in three classrooms during two measuring campaigns, which together encompassed a period of 60 days. Initial investigations showed that under the normal operating conditions of the school there were many occasions in all three classrooms where indoor particle concentrations increased significantly compared to outdoor levels. By far the highest increases in the classroom resulted from art activities (painting, gluing and drawing), at times reaching over 1.4 x 105 particle cm-3. The indoor particle concentrations exceeded outdoor concentrations by approximately one order of magnitude, with a count median diameter ranging from 20-50 nm. Significant increases also occurred during cleaning activities, when detergents were used. GC-MS analysis conducted on 4 samples randomly selected from about 30 different paints and glues, as well as the detergent used in the school, showed that d-limonene was one of the main organic compounds of the detergent, however, it was not detected in the samples of the paints and the glue. Controlled experiments showed that this monoterpene, emitted from the detergent, reacted with O3 (at outdoor ambient concentrations ranging from 0.06-0.08ppm) and formed secondary organic aerosols. Further investigations to identify other liquids which may be potential sources of the precursors of secondary organic aerosols, were outside the scope of this project, however, it is expected that the problem identified by this study could be more widely spread, since most primary schools use liquid materials for art classes, and all schools use detergents for cleaning. Further studies are therefore recommended to better understand this phenomenon and also to minimize school children exposure to ultrafine particles from these indoor sources.

Utilisation of seed resources by small mammals : a two-way interaction

Within the Australian wet tropics bioregion, only 900 000 hectares of once continuous rainforest habitat between Townsville and Cooktown now remains. While on the Atherton Tableland, only 4% of the rainforest that once occurred there remains today with remnant vegetation now forming a matrix of rainforest dispersed within agricultural land (sugarcane, banana, orchard crops, townships and pastoral land). Some biologists have suggested that remnants often support both faunal and floral communities that differ significantly from remaining continuous forest. Australian tropical forests possess a relatively high diversity of native small mammal species particularly rodents, which unlike larger mammalian and avian frugivores elsewhere, have been shown to be resilient to the effects of fragmentation, patch isolation and reduction in patch size. While small mammals often become the dominant mammalian frugivores, in terms of their relative abundance, the relationship that exists between habitat diversity and structure, and the impacts of small mammal foraging within fragmented habitat patches in Australia, is still poorly understood. The relationship between foraging behaviour and demography of two small mammal species, Rattus fuscipes and Melomys cervinipes, and food resources in fragmented rainforest sites, were investigated in the current study. Population densities of both species were strongly related with overall density of seed resources in all rainforest fragments. The distribution of both mammal species however, was found to be independent of the distribution of seed resources. Seed utilisation trials indicated that M.cervinipes and R.fuscipes had less impact on seed resources (extent of seed harvesting) than did other rainforest frugivores. Experimental feeding trials demonstrated that in 85% of fruit species tested, rodent feeding increased seed germination by a factor of 3.5 suggesting that in Australian tropical rainforest remnants, small mammals may play a significant role in enhancing germination of large seeded fruits. This study has emphasised the role of small mammals in tropical rainforest systems in north eastern Australia, in particular, the role that they play within isolated forest fragments where larger frugivorous species may be absent.

Dynamics of transformation and fragmentation of composite liquid nano-particles

Recent research on particle size distributions and particle concentrations near a busy road cannot be explained by the conventional mechanisms for particle evolution of combustion aerosols. Specifically they appear to be inadequate to explain the experimental observations of particle transformation and the evolution of the total number concentration. This resulted in the development of a new mechanism based on their thermal fragmentation, for the evolution of combustion aerosol nano-particles. A complex and comprehensive pattern of evolution of combustion aerosols, involving particle fragmentation, was then proposed and justified. In that model it was suggested that thermal fragmentation occurs in aggregates of primary particles each of which contains a solid graphite/carbon core surrounded by volatile molecules bonded to the core by strong covalent bonds. Due to the presence of strong covalent bonds between the core and the volatile (frill) molecules, such primary composite particles can be regarded as solid, despite the presence of significant (possibly, dominant) volatile component. Fragmentation occurs when weak van der Waals forces between such primary particles are overcome by their thermal (Brownian) motion. In this work, the accepted concept of thermal fragmentation is advanced to determine whether fragmentation is likely in liquid composite nano-particles. It has been demonstrated that at least at some stages of evolution, combustion aerosols contain a large number of composite liquid particles containing presumably several components such as water, oil, volatile compounds, and minerals. It is possible that such composite liquid particles may also experience thermal fragmentation and thus contribute to, for example, the evolution of the total number concentration as a function of distance from the source. Therefore, the aim of this project is to examine theoretically the possibility of thermal fragmentation of composite liquid nano-particles consisting of immiscible liquid v components. The specific focus is on ternary systems which include two immiscible liquid droplets surrounded by another medium (e.g., air). The analysis shows that three different structures are possible, the complete encapsulation of one liquid by the other, partial encapsulation of the two liquids in a composite particle, and the two droplets separated from each other. The probability of thermal fragmentation of two coagulated liquid droplets is discussed and examined for different volumes of the immiscible fluids in a composite liquid particle and their surface and interfacial tensions through the determination of the Gibbs free energy difference between the coagulated and fragmented states, and comparison of this energy difference with the typical thermal energy kT. The analysis reveals that fragmentation was found to be much more likely for a partially encapsulated particle than a completely encapsulated particle. In particular, it was found that thermal fragmentation was much more likely when the volume ratio of the two liquid droplets that constitute the composite particle are very different. Conversely, when the two liquid droplets are of similar volumes, the probability of thermal fragmentation is small. It is also demonstrated that the Gibbs free energy difference between the coagulated and fragmented states is not the only important factor determining the probability of thermal fragmentation of composite liquid particles. The second essential factor is the actual structure of the composite particle. It is shown that the probability of thermal fragmentation is also strongly dependent on the distance that each of the liquid droplets should travel to reach the fragmented state. In particular, if this distance is larger than the mean free path for the considered droplets in the air, the probability of thermal fragmentation should be negligible. In particular, it follows form here that fragmentation of the composite particle in the state with complete encapsulation is highly unlikely because of the larger distance that the two droplets must travel in order to separate. The analysis of composite liquid particles with the interfacial parameters that are expected in combustion aerosols demonstrates that thermal fragmentation of these vi particles may occur, and this mechanism may play a role in the evolution of combustion aerosols. Conditions for thermal fragmentation to play a significant role (for aerosol particles other than those from motor vehicle exhaust) are determined and examined theoretically. Conditions for spontaneous transformation between the states of composite particles with complete and partial encapsulation are also examined, demonstrating the possibility of such transformation in combustion aerosols. Indeed it was shown that for some typical components found in aerosols that transformation could take place on time scales less than 20 s. The analysis showed that factors that influenced surface and interfacial tension played an important role in this transformation process. It is suggested that such transformation may, for example, result in a delayed evaporation of composite particles with significant water component, leading to observable effects in evolution of combustion aerosols (including possible local humidity maximums near a source, such as a busy road). The obtained results will be important for further development and understanding of aerosol physics and technologies, including combustion aerosols and their evolution near a source.