The application of a profluorescent nitroxide probe to detect reactive oxygen species derived from combustion-generated particulate matter

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.

Indoor and outdoor nitrogen dioxide concentration in residential houses in Australia

As part of a larger indoor environmental study, residential indoor and outdoor levels of nitrogen dioxide (NO2) were measured for 14 houses in a suburb of Brisbane, Queensland, Australia. Passive samplers were used for 48-h sampling periods during the winter of 1999. The average indoor and outdoor NO2 levels were 13.8 ± 6.3 and 16.7 ± 4.2 ppb, respectively. The indoor/outdoor NO2 concentration ratio ranged from 0.4 to 2.3, with a median value of 0.82. The results of statistic analyses indicated that there was no significant correlation between indoor and outdoor NO2 concentrations, or between indoor and fixed site NO2 monitoring station concentrations. However, there was a significant correlation between outdoor and fixed site NO2 monitoring station concentrations. There was also a significant correlation between indoor NO2 concentration and indoor submicrometre (0.007–0.808 μm) aerosol particle number concentrations. The results in this study indicated indoor NO2 levels are significantly affected by indoor NO2 sources, such as a gas stove and cigarette smoking. It implies that the outdoor or fixed site monitoring concentration alone is a poor predictor of indoor NO2 concentration.

Local Rademacher complexities

We propose new bounds on the error of learning algorithms in terms of a data-dependent notion of complexity. The estimates we establish give optimal rates and are based on a local and empirical version of Rademacher averages, in the sense that the Rademacher averages are computed from the data, on a subset of functions with small empirical error. We present some applications to classification and prediction with convex function classes, and with kernel classes in particular.

Turbulent velocity and suspended sediment concentration measurements in an urban environment of the Brisbane River Flood Plain at Gardens Point on 12-13 January 2011

The flood flow in urbanised areas constitutes a major hazard to the population and infrastructure as seen during the summer 2010-2011 floods in Queensland (Australia). Flood flows in urban environments have been studied relatively recently, although no study considered the impact of turbulence in the flow. During the 12-13 January 2011 flood of the Brisbane River, some turbulence measurements were conducted in an inundated urban environment in Gardens Point Road next to Brisbane's central business district (CBD) at relatively high frequency (50 Hz). The properties of the sediment flood deposits were characterised and the acoustic Doppler velocimeter unit was calibrated to obtain both instantaneous velocity components and suspended sediment concentration in the same sampling volume with the same temporal resolution. While the flow motion in Gardens Point Road was subcritical, the water elevations and velocities fluctuated with a distinctive period between 50 and 80 s. The low frequency fluctuations were linked with some local topographic effects: i.e, some local choke induced by an upstream constriction between stairwells caused some slow oscillations with a period close to the natural sloshing period of the car park. The instantaneous velocity data were analysed using a triple decomposition, and the same triple decomposition was applied to the water depth, velocity flux, suspended sediment concentration and suspended sediment flux data. The velocity fluctuation data showed a large energy component in the slow fluctuation range. For the first two tests at z = 0.35 m, the turbulence data suggested some isotropy. At z = 0.083 m, on the other hand, the findings indicated some flow anisotropy. The suspended sediment concentration (SSC) data presented a general trend with increasing SSC for decreasing water depth. During a test (T4), some long -period oscillations were observed with a period about 18 minutes. The cause of these oscillations remains unknown to the authors. The last test (T5) took place in very shallow waters and high suspended sediment concentrations. It is suggested that the flow in the car park was disconnected from the main channel. Overall the flow conditions at the sampling sites corresponded to a specific momentum between 0.2 to 0.4 m2 which would be near the upper end of the scale for safe evacuation of individuals in flooded areas. But the authors do not believe the evacuation of individuals in Gardens Point Road would have been safe because of the intense water surges and flow turbulence. More generally any criterion for safe evacuation solely based upon the flow velocity, water depth or specific momentum cannot account for the hazards caused by the flow turbulence, water depth fluctuations and water surges.

SwarmPS: Rapid, semi-automated single particle selection software

Single particle analysis (SPA) coupled with high-resolution electron cryo-microscopy is emerging as a powerful technique for the structure determination of membrane protein complexes and soluble macromolecular assemblies. Current estimates suggest that ∼104–105 particle projections are required to attain a 3 Å resolution 3D reconstruction (symmetry dependent). Selecting this number of molecular projections differing in size, shape and symmetry is a rate-limiting step for the automation of 3D image reconstruction. Here, we present SwarmPS, a feature rich GUI based software package to manage large scale, semi-automated particle picking projects. The software provides cross-correlation and edge-detection algorithms. Algorithm-specific parameters are transparently and automatically determined through user interaction with the image, rather than by trial and error. Other features include multiple image handling (∼102), local and global particle selection options, interactive image freezing, automatic particle centering, and full manual override to correct false positives and negatives. SwarmPS is user friendly, flexible, extensible, fast, and capable of exporting boxed out projection images, or particle coordinates, compatible with downstream image processing suites.

An epistemic community as influencer and implementer in local government accounting in Australia

This paper adopts an epistemic community framework to explicate the dual role of epistemic communities as influencers of accounting policy within regulatory space and as implementers who effect change within the domain of accounting. The context is the adoption and implementation of fair value accounting within local government in New South Wales (NSW). The roles and functions of Australian local government are extensive, and include the development and maintenance of infrastructure, provision of recreational facilities, certain health and community services, buildings, cultural facilities, and in some cases, water and sewerage (Australian Local Government Association, 2009). The NSW state Department of Local Government (DLG) is responsible for legislation and policy development to ensure that local councils are able to deliver ‘quality services to their communities in a sustainable manner’ (DLG, 2008c). These local councils receive revenue from various sources including property rates, government grants and user-pays service provision. In July 2006 the DLG issued Circular 06-453 to councils (DLG, 2006c), mandating the staged adoption of fair value measurement of infrastructure assets. This directive followed the policy of NSW State Treasury (NSW Treasury, 2007),4 and an independent inquiry into the financial sustainability of local councils (LGSA, 2006). It was an attempt to resolve the inconsistency in public sector asset valuation in NSW Local Governments, and to provide greater usefulness and comparability of financial statements.5 The focus of this study is the mobilization of accounting change by the DLG within this wider political context. When a regulatory problem arises, those with political power seek advice from professionals with relevant skill and expertise (Potter, 2005). This paper explores the way in which professionals diffuse accounting ‘problems’ and the associated accounting solutions ‘across time and space’ (Potter, 2005, p. 277). The DLG’s fair value accounting policy emanated from a ‘regulatory space’ (Hancher and Moran, 1989)6 as a result of negotiations between many parties, including accounting and finance professionals. Operating within the local government sector, these professionals were identified by the DLG as being capable of providing helpful input. They were also responsible for the implementation of the new olicy within local councils. Accordingly they have been dentified as an pistemic community with the ability to ranslate regulatory power by changing he domain of ccounting (Potter, 2005, p. 278).7 The paper is organised as follows. The background to the LG’s decision to require the introduction of fair value accounting for infrastructure assets is explored. Following this, the method of the study is described, and the epistemic community framework outlined. In the next sections, evidence of the influencing and implementing roles of epistemic groups is provided. Finally, conclusions are drawn about the significance of these groups both within regulatory space in developing accounting regulation, and in embedding change within the domain of accounting.

Ozone-initiated particle formation, particle aging, and precursors in a laser printer

An increasing number of researchers have hypothesized that ozone may be involved in the particle formation processes that occur during printing, however no studies have investigated this further. In the current study, this hypothesis was tested in a chamber study by adding supplemental ozone to the chamber after a print job without measurable ozone emissions. Subsequent particle number concentration and size distribution measurements showed that new particles were formed minutes after the addition of ozone. The results demonstrated that ozone did react with printer-generated volatile organic compounds (VOCs) to form secondary organic aerosols (SOAs). The hypothesis was further confirmed by the observation of correlations among VOCs, ozone, and particles concentrations during a print job with measurable ozone emissions. The potential particle precursors were identified by a number of furnace tests, which suggested that squalene and styrene were the most likely SOA precursors with respect to ozone. Overall, this study significantly improved scientific understanding of the formation mechanisms of printer-generated particles, and highlighted the possible SOA formation potential of unsaturated nonterpene organic compounds by ozone-initiated reactions in the indoor environment. © 2011 American Chemical Society.

Measurements of particle emissions from nanotechnology processes, with assessment of measuring techniques and workplace controls

The overall aim of this project was to contribute to existing knowledge regarding methods for measuring characteristics of airborne nanoparticles and controlling occupational exposure to airborne nanoparticles, and to gather data on nanoparticle emission and transport in various workplaces. The scope of this study involved investigating the characteristics and behaviour of particles arising from the operation of six nanotechnology processes, subdivided into nine processes for measurement purposes. It did not include the toxicological evaluation of the aerosol and therefore, no direct conclusion was made regarding the health effects of exposure to these particles. Our research included real-time measurement of sub, and supermicrometre particle number and mass concentration, count median diameter, and alveolar deposited surface area using condensation particle counters, an optical particle counter, DustTrak photometer, scanning mobility particle sizer, and nanoparticle surface area monitor, respectively. Off-line particle analysis included scanning and transmission electron microscopy, energy-dispersive x-ray spectrometry, and thermal optical analysis of elemental carbon. Sources of fibrous and non-fibrous particles were included.

Airborne particle concentrations at schools measured at different spatial scales

Potential adverse effects on children health may result from school exposure to airborne particles. To address this issue, measurements in terms of particle number concentration, particle size distribution and black carbon (BC) concentrations were performed in three school buildings in Cassino (Italy) and its suburbs, outside and inside of the classrooms during normal occupancy and use. Additional time resolved information was gathered on ventilation condition, classroom activity, and traffic count data around the schools were obtained using a video camera. Across the three investigated school buildings, the outdoor and indoor particle number concentration monitored down to 4 nm and up to 3 m ranged from 2.8×104 part cm-3 to 4.7×104 part cm-3 and from 2.0×104 part cm-3 to 3.5×104 part cm-3, respectively. The total particle concentrations were usually higher outdoors than indoors, because no indoor sources were detected. I/O measured was less than 1 (varying in a relatively narrow range from 0.63 to 0.74), however one school exhibited indoor concentrations higher than outdoor during the morning rush hours. Particle size distribution at the outdoor site showed high particle concentrations in different size ranges, varying during the day; in relation to the starting and finishing of school time two modes were found. BC concentrations were 5 times higher at the urban school compared with the suburban and suburban-to-urban differences were larger than the relative differences of ultrafine particle concentrations.

Inhaled particle counts on bicycle commute routes of low and high proximity to motorised traffic

Frequent exposure to ultrafine particles (UFP) is associated with detrimental effects on cardiopulmonary function and health. UFP dose and therefore the associated health risk are a factor of exposure frequency, duration, and magnitude of (therefore also proximity to) a UFP emission source. Bicycle commuters using on-road routes during peak traffic times are sharing a microenvironment with high levels of motorised traffic, a major UFP emission source. Inhaled particle counts were measured along popular pre-identified bicycle commute route alterations of low (LOW) and high (HIGH) motorised traffic to the same inner-city destination at peak commute traffic times. During commute, real-time particle number concentration (PNC; mostly in the UFP range) and particle diameter (PD), heart and respiratory rate, geographical location, and meteorological variables were measured. To determine inhaled particle counts, ventilation rate was calculated from heart-rate-ventilation associations, produced from periodic exercise testing. Total mean PNC of LOW (compared to HIGH) was reduced (1.56 x e4 ± 0.38 x e4 versus 3.06 x e4 ± 0.53 x e4 ppcc; p = 0.012). Total estimated ventilation rate did not vary significantly between LOW and HIGH (43 ± 5 versus 46 ± 9 L•min; p = 0.136); however, due to total mean PNC, accumulated inhaled particle counts were 48% lower in LOW, compared to HIGH (7.6 x e8 ± 1.5 x e8 versus 14.6 x e8 ± 1.8 x e8; p = 0.003). For bicycle commuting at peak morning commute times, inhaled particle counts and therefore cardiopulmonary health risk may be substantially reduced by decreasing exposure to motorised traffic, which should be considered by both bicycle commuters and urban planners.

Accurate stratospheric particle-size distributions from a flat-plate collection surface

The first representative chemical, structural, and morphological analysis of the solid particles from a single collection surface has been performed. This collection surface sampled the stratosphere between 17 and 19km in altitude in the summer of 1981, and therefore before the 1982 eruptions of El Chichón. A particle collection surface was washed free of all particles with rinses of Freon and hexane, and the resulting wash was directed through a series of vertically stacked Nucleopore filters. The size cutoff for the solid particle collection process in the stratosphere is found to be considerably less than 1 μm. The total stratospheric number density of solid particles larger than 1μm in diameter at the collection time is calculated to be about 2.7×10−1 particles per cubic meter, of which approximately 95% are smaller than 5μm in diameter. Previous classification schemes are expanded to explicitly recognize low atomic number material. With the single exception of the calcium-aluminum-silicate (CAS) spheres all solid particle types show a logarithmic increase in number concentration with decreasing diameter. The aluminum-rich particles are unique in showing bimodal size distributions. In addition, spheres constitute only a minor fraction of the aluminum-rich material. About 2/3 of the particles examined were found to be shards of rhyolitic glass. This abundant volcanic material could not be correlated with any eruption plume known to have vented directly to the stratosphere. The micrometeorite number density calculated from this data set is 5×10−2 micrometeorites per cubic meter of air, an order of magnitude greater than the best previous estimate. At the collection altitude, the maximum collision frequency of solid particles >5μm in average diameter is calculated to be 6.91×10−16 collisions per second, which indicates negligible contamination of extraterrestrial particles in the stratosphere by solid anthropogenic particles.

Investigation of the airborne submicrometer particles emitted by dredging vessels using a plume capture method

This paper presents a method for investigating ship emissions, the plume capture and analysis system (PCAS), and its application in measuring airborne pollutant emission factors (EFs) and particle size distributions. The current investigation was conducted in situ, aboard two dredgers (Amity: a cutter suction dredger and Brisbane: a hopper suction dredger) but the PCAS is also capable of performing such measurements remotely at a distant point within the plume. EFs were measured relative to the fuel consumption using the fuel combustion derived plume CO2. All plume measurements were corrected by subtracting background concentrations sampled regularly from upwind of the stacks. Each measurement typically took 6 minutes to complete and during one day, 40 to 50 measurements were possible. The relationship between the EFs and plume sample dilution was examined to determine the plume dilution range over which the technique could deliver consistent results when measuring EFs for particle number (PN), NOx, SO2, and PM2.5 within a targeted dilution factor range of 50-1000 suitable for remote sampling. The EFs for NOx, SO2, and PM2.5 were found to be independent of dilution, for dilution factors within that range. The EF measurement for PN was corrected for coagulation losses by applying a time dependant particle loss correction to the particle number concentration data. For the Amity, the EF ranges were PN: 2.2 - 9.6 × 1015 (kg-fuel)-1; NOx: 35-72 g(NO2).(kg-fuel)-1, SO2 0.6 - 1.1 g(SO2).(kg-fuel)-1and PM2.5: 0.7 – 6.1 g(PM2.5).(kg-fuel)-1. For the Brisbane they were PN: 1.0 – 1.5 x 1016 (kg-fuel)-1, NOx: 3.4 – 8.0 g(NO2).(kg-fuel)-1, SO2: 1.3 – 1.7 g(SO2).(kg-fuel)-1 and PM2.5: 1.2 – 5.6 g(PM2.5).(kg-fuel)-1. The results are discussed in terms of the operating conditions of the vessels’ engines. Particle number emission factors as a function of size as well as the count median diameter (CMD), and geometric standard deviation of the size distributions are provided. The size distributions were found to be consistently uni-modal in the range below 500 nm, and this mode was within the accumulation mode range for both vessels. The representative CMDs for the various activities performed by the dredgers ranged from 94-131 nm in the case of the Amity, and 58-80 nm for the Brisbane. A strong inverse relationship between CMD and EF(PN) was observed.

Utility of an alternative bicycle commute route of lower proximity to motorised traffic in decreasing exposure to ultra-fine particles, respiratory symptoms and airway inflammation - a structured exposure experiment

Background: Bicycle commuting in an urban environment of high air pollution is known as a potential health risk, especially for susceptible individuals. While risk management strategies aimed to reduce motorised traffic emissions exposure have been suggested, limited studies have assessed the utility of such strategies in real-world circumstances. Objectives: The potential of reducing exposure to ultrafine particles (UFP; < 0.1 µm) during bicycle commuting by lowering interaction with motorised traffic was investigated with real-time air pollution and acute inflammatory measurements in healthy individuals using their typical, and an alternative to their typical, bicycle commute route. Methods: Thirty-five healthy adults (mean ± SD: age = 39 ± 11 yr; 29% female) each completed two return trips of their typical route (HIGH) and a pre-determined altered route of lower interaction with motorised traffic (LOW; determined by the proportion of on-road cycle paths). Particle number concentration (PNC) and diameter (PD) were monitored in real-time in-commute. Acute inflammatory indices of respiratory symptom incidence, lung function and spontaneous sputum (for inflammatory cell analyses) were collected immediately pre-commute, and one and three hours post-commute. Results: LOW resulted in a significant reduction in mean PNC (1.91 x e4 ± 0.93 x e4 ppcc vs. 2.95 x e4 ± 1.50 x e4 ppcc; p ≤ 0.001). Besides incidence of in-commute offensive odour detection (42 vs. 56 %; p = 0.019), incidence of dust and soot observation (33 vs. 47 %; p = 0.038) and nasopharyngeal irritation (31 vs. 41 %; p = 0.007), acute inflammatory indices were not significantly associated to in-commute PNC, nor were these indices reduced with LOW compared to HIGH. Conclusions: Exposure to PNC, and the incidence of offensive odour and nasopharyngeal irritation, can be significantly reduced when utilising a strategy of lowering interaction with motorised traffic whilst bicycle commuting, which may bring important benefits for both healthy and susceptible individuals.

Composition and morphology of particle emissions from in-use aircraft during takeoff and landing

In order to provide realistic data for air pollution inventories and source apportionment at airports, the morphology and composition of ultrafine particles (UFP) in aircraft engine exhaust were measured and characterized. For this purpose, two independent measurement techniques were employed to collect emissions during normal takeoff and landing operations at Brisbane Airport, Australia. PM1 emissions in the airfield were collected on filters and analyzed using the particle-induced X-ray emission (PIXE) technique. Morphological and compositional analyses of individual ultrafine particles in aircraft plumes were performed on silicon nitride membrane grids using transmission electron microscopy (TEM) combined with energy-dispersive X-ray microanalysis (EDX). TEM results showed that the deposited particles were in the range of 5 to 100 nm in diameter, had semisolid spherical shapes and were dominant in the nucleation mode (18 – 20 nm). The EDX analysis showed the main elements in the nucleation particles were C, O, S and Cl. The PIXE analysis of the airfield samples was generally in agreement with the EDX in detecting S, Cl, K, Fe and Si in the particles. The results of this study provide important scientific information on the toxicity of aircraft exhaust and their impact on local air quality.