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.

Recovery and reuse of ammonium from wastewater treatment plants : an application for agriculture

In wastewater treatment plants based on anaerobic digestion, supernatant and outflows from sludge dewatering systems contain significantly high amount of ammonium. Generally, these waters are returned to the head of wastewater treatment plant (WWTP), thereby increasing the total nitrogen load of the influent flow. Ammonium from these waters can be recovered and commercially utilised using novel ion-exchange materials. Mackinnon et al. have described an approach for removal and recovery of ammonium from side stream centrate returns obtained from anaerobic digester of a typical WWTP. Most of the ammonium from side streams can potentially be removed, which significantly reduces overall inlet demand at a WWTP. However, the extent of reduction achieved depends on the level of ammonium and flow-rate in the side stream. The exchange efficiency of the ion-exchange material, MesoLite, used in the ammonium recovery process deteriorates with long-term use due to mechanical degradation and use of regenerant. To ensure that a sustainable process is utilised a range of potential applications for this “spent” MesoLite have been evaluated. The primary focus of evaluations has been use of ammonium-loaded MesoLite as a source of nitrogen and growth medium for plants. A MesoLite fertiliser has advantage over soluble fertilisers in that N is held on an insoluble matrix and is gradually released according to exchange equilibria. Many conventional N fertilisers are water-soluble and thus, instantly release all applied N into the soil solution. Loss of nutrient commonly occurs through volatilisation and/or leaching. On average, up to half of the N delivered by a typical soluble fertiliser can be lost through these processes. In this context, use of ammonium-loaded MesoLite as a fertiliser has been evaluated using standard greenhouse and field-based experiments for low fertility soils. Rye grass, a suitable test species for greenhouse trials, was grown in 1kg pots over a period of several weeks with regular irrigation. Nitrogen was applied at a range of rates using a chemical fertiliser as a control and using two MesoLite fertilisers. All other nutrients were applied in adequate amounts. All treatments were replicated three times. Plants were harvested after four weeks, and dry plant mass and N concentrations were determined. At all nitrogen application rates, ammonium-loaded MesoLite produced higher plant mass than plants fertilised by the chemical fertiliser. The lower fertiliser effectiveness of the chemical fertliser is attributed to possible loss of some N through volatilisation. The MesoLite fertilisers did not show any adverse effect on availability of macro and trace nutrients, as shown by lack of deficiency symptoms, dry matter yield and plant analyses. Nitrogen loaded on to MesoLite in the form of exchanged ammonium is readily available to plants while remaining protected from losses via leaching and volatilisation. Spent MesoLite appears to be a suitable and effective fertiliser for a wide range of soils, particularly sandy soils with poor nutrient holding capacity.

Designing learning spaces for (partially) online lives : recombinant architecture

The notion of recombinant architecture signals a loosening of spatial connections between physical and digital-online environments (Mitchell, 1996; 2000; 2003). Such an idea also points to the transformative nature of the designing approaches concerned with the creation of spaces where bits meet bodies to fulfil human needs and desires and, at the same time, pursuing those human dimensions of space and place which are so important to our senses of belonging, physical comfort and amenity. This paper proposes that recombinant spaces and places draw on familiar architectural forms and functions and on the transforming functions of digital-online modes. Perspectives, approaches and resources outlined in the paper support designing and re-designing enterprises and aim to stimulate discussion in the Digital Environments strand of this online conference: 'Under Construction: a world without walls'.

On the (partially) inalienable rights of participants in virtual communities

As virtual communities become more central to the everyday activities of connected individuals, we face increasingly pressing questions about the proper allocation of power, rights and responsibilities. This paper argues that our current legal discourse is ill-equipped to provide answers that will safeguard the legitimate interests of participants and simultaneously refrain from limiting the future innovative development of these spaces. From social networking sites like Facebook to virtual worlds like World of Warcraft and Second Life, participants who are banned from these communities stand to lose their virtual property, their connections to their friends and family, and their personal expression. Because our legal system views the proprietor’s interests as absolute private property rights, however, participants who are arbitrarily, capriciously or maliciously ejected have little recourse under law. This paper argues that, rather than assuming that a private property and freedom of contract model will provide the most desirable outcomes, a more critical approach is warranted. By rejecting the false dichotomy between ‘public’ and ‘private’ spaces, and recognising some of the absolutist and necessitarian trends in the current property debate, we may be able to craft legal rules that respect the social bonds between participants while simultaneously protecting the interests of developers.

Characterisation of soluble components and PAH in PM10 atmospheric particulate matter in Brisbane

Fours sets of PM10 samples were collected in three sites in SEQ from December 2002 to August 2004. Three of these sets of samples were collected by QLD EPA as a part of their regular air monitoring program at Woolloongabba, Rocklea and Eagle Farm. Half of the samples were used in this study for the analysis of water-soluble ions, which are Na+, K+, Mg2+, Ca2+, NH4 +, Cl-, NO3 -, SO4 2-, F-, Br-, NO2 -, PO4 -3 and the other half was retained by QLD EPA. The fourth set of samples was collected at Rocklea, specifically for this study. A quarter of the samples obtained from this set of samples were used to analyse water-soluble ions; a quarter of the sample was used to analyse Pb, Cu, Al, Fe, Mn and Zn; and the rests were used to analyse US EPA 16 priority PAHs. The water-soluble ions were extracted ultrasonically with water and the major watersoluble anions as well as NH4 + were analysed using IC. Na+, K+, Mg2+, Ca2+ Pb, Cu, Al, Fe, Mn and Zn were analysed using ICP-AES while PAHs were extracted by acetonitrile and analysed using HPLC. Of the analysed water-soluble ions, Cl-, NO3 -, SO4 2-, Na+, K+, Mg2+ and Ca2+ were high in concentration and determined in all the samples. F-, Br-, NO2 -, PO4 -3 and NH4 + ions were lower in concentration and determined only in some samples. Na+ and Cl- were high in all samples indicating the importance of a marine source. Principal Component Analysis (PCA) was used to examine the temporal variations of the water-soluble ions at the three sites. The results indicated that there was no major difference between the three sites. However, comparing the average concentrations of ions and Cl-/Na+ it was concluded that Woolloongabba had more marine influence than the other sites. Al, Fe and Zn were detected in all samples. Al and Fe were high in all samples indicating the significance of a source of crustal matter. Cu, Mn and Pb were in low concentrations and were determined only in some samples. The lower Pb concentrations observed in the study than in previous studies indicate that the phasing-out of leaded petrol had an appreciable impact on Pb levels in SEQ. This study reports for the first time, simultaneous data on the water-soluble, metal ion and PAH levels of PM10 aerosols in Brisbane, and provides information on the most likely sources of these chemical species. Such information can be used alongside those that already exist to formulate PM10 pollution reduction strategies for SEQ in order to protect the community from the adverse effects of PM pollution.

Discovery and characterization of IGFBP-mediated endocytosis in the human retinal pigment epithelial cell line ARPE-19

Insulin-like growth factor binding proteins (IGFBPs) are prime regulators of IGF-action in numerous cell types including the retinal pigment epithelium (RPE). The RPE performs several functions essential for vision, including growth factor secretion and waste removal via a phagocytic process mediated in part by vitronectin (Vn). In the course of studying the effects of IGFBPs on IGF-mediated VEGF secretion and Vn-mediated phagocytosis in the RPE cell line ARPE-19, we have discovered that these cells avidly ingest synthetic microspheres (2.0 μm diameter) coated with IGFBPs. Given the novelty of this finding and the established role for endocytosis in mediating IGFBP actions in other cell types, we have explored the potential role of candidate cell surface receptors. Moreover, we have examined the role of key IGFBP structural motifs, by comparing responses to three members of the IGFBP family (IGFBP-3, IGFBP-4 and IGFBP-5) which display overlapping variations in primary structure and glycosylation status. Coating of microspheres (FluoSpheres®, sulfate modified polystyrene filled with a fluorophore) was conducted at 37 °C for 1 h using 20 μg/mL of test protein, followed by extensive washing. Binding of proteins was confirmed using a microBCA assay. The negative control consisted of microspheres treated with 0.1% bovine serum albumin (BSA), and all test samples were post-treated with BSA in an effort to coat any remaining free protein binding sites, which might otherwise encourage non-specific interactions with the cell surface. Serum-starved cultures of ARPE-19 cells were incubated with microspheres for 24 h, using a ratio of approximately 100 microspheres per cell. Uptake of microspheres was quantified using a fluorometer and was confirmed visually by confocal fluorescence microscopy. The ARPE-19 cells displayed little affinity for BSA-treated microspheres, but avidly ingested large quantities of those pre-treated with Vn (ANOVA; p < 0.001). Strong responses were also observed towards recombinant formulations of non-glycosylated IGFBP-3, glycosylated IGFBP-3 and glycosylated IGFBP-5 (all p < 0.001), while glycosylated IGFBP-4 induced a relatively minor response (p < 0.05). The response to IGFBP-3 was unaffected in the presence of excess soluble IGFBP-3, IGF-I or Vn. Likewise, soluble IGFBP-3 did not induce uptake of BSA-treated microspheres. Antibodies to either the transferrin receptor or type 1 IGF-receptor displayed slight inhibitory effects on responses to IGFBPs and Vn. Heparin abolished responses to Vn, IGFBP-5 and non-glycosylated IGFBP-3, but only partially inhibited the response to glycosylated IGFBP-3. Our results demonstrate for the first time IGFBP-mediated endocytosis in ARPE-19 cells and suggest roles for the IGFBP-heparin-binding domain and glycosylation status. These findings have important implications for understanding the mechanisms of IGFBP actions on the RPE, and in particular suggest a role for IGFBP-endocytosis.

Dust emissions from a tunnel-ventilated broiler poultry shed with fresh and partially reused litter

Dust emissions from large-scale, tunnel-ventilated poultry sheds could have negative health and environmental impacts. Despite this fact, the literature concerning dust emissions from tunnel-ventilated poultry sheds in Australia and overseas is relatively scarce. Dust measurements were conducted during two consecutive production cycles at a single broiler shed on a poultry farm near Ipswich, Queensland. Fresh litter was employed during the first cycle and partially reused litter was employed during the second cycle. This provided an opportunity to study the effect that partial litter reuse has on dust emissions. Dust levels were characterised by the number concentration of suspended particles having diameter between 0.5–20 μm and by the mass concentration of dust particles below 10 μm diameter (PM10) and 2.5 μm diameter (PM2.5). In addition, we measured the number size distributions of dust particles. The average concentration and emission rate of dust was higher when partially reused litter was used in the shed than when fresh litter was used. In addition we found that dust particles emitted from the shed with partially reused litter were finer than the particles emitted with fresh litter. Although the change in litter properties is certainly contributing to this observed variability, other factors such as ventilation rate and litter moisture content are also likely to be involved.

Alexithymia in alcohol dependent patients is partially mediated by alcohol expectancy

Background: Up to fifty percent of alcohol dependent individuals have alexithymia, a personality trait characterised by difficulties identifying and describing feelings, a lack of imagination and an externalised cognitive style. Although studies have examined alexithymia in relation to alcohol dependence, no research exists on mechanisms underlying this relationship. The present study examined the mediational effect of alcohol expectancies on alexithymia and alcohol dependence.----- ----- Methods: 230 outpatients completed the Toronto Alexithymia Scale (TAS-20), the Drinking Expectancy Questionnaire (DEQ) and the Alcohol Use Disorder Identification Test (AUDIT). Results: Regression analysis showed that alexithymia and alcohol dependence was, in two of three cases, partially mediated through alcohol expectancy.----- ----- Conclusions: Alcohol expectancies of assertion and affective change show promise as mediators of alcohol dependence in individuals with alexithymia.

Effect of spacing of reinforcement on the behaviour of partially grouted masonry shear walls

Partially Grouted Reinforced Masonry (PGRM) shear walls perform well in places where the cyclonic wind pressure dominates the design. Their out-of-plane flexural performance is better understood than their inplane shear behaviour; in particular, it is not clear whether the PGRM shear walls act as unreinforced masonry (URM) walls embedded with discrete reinforced grouted cores or as integral systems of reinforced masonry (RM) with wider spacing of reinforcement. With a view to understanding the inplane response of PGRM shear walls, ten full scale single leaf, clay block walls were constructed and tested under monotonic and cyclic inplane loading cases. It has been shown that where the spacing of the vertical reinforcement is less than 2000mm, the walls behave as an integral system of RM; for spacing greater than 2000mm, the walls behave similar to URM with no significant benefit from the reinforced cores based on the displacement ductility and stiffness degradation factors derived from the complete lateral load – lateral displacement curves.

Advances in heterogeneous photocatalytic degradation of phenols and dyes in wastewater : a review

The heterogeneous photocatalytic water purification process has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible light spectrum. This paper aims to review and summarize the recently published works in the field of photocatalytic oxidation of toxic organic compounds such as phenols and dyes, predominant in waste water effluent. In this review, the effects of various operating parameters on the photocatalytic degradation of phenols and dyes are presented. Recent findings suggested that different parameters, such as type of photocatalyst and composition, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidizing agents/electron acceptors, mode of catalyst application, and calcinations temperature can play an important role on the photocatlytic degradation of organic compounds in water environment. Extensive research has focused on the enhancement of photocatalysis by modification of TiO2 employing metal, non-metal and ion doping. Recent advances in TiO2 photocatalysis for the degradation of various phenols and dyes are also highlighted in this review.

Influence of parameters on the heterogeneous photocatalytic degradation of pesticides and phenolic contaminants in wastewater : a short review

In recent years, the application of heterogeneous photocatalytic water purification process has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible light spectrum. This paper aims to review and summarize the recently published works on the titanium dioxide (TiO2) photocatalytic oxidation of pesticides and phenolic compounds, predominant in storm and waste water effluents. The effect of various operating parameters on the photocatalytic degradation of pesticides and phenols are discussed. Results reported here suggested that the photocatalytic degradation of organic compounds depends on the type of photocatalyst and composition, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidizing agents/electron acceptors, catalyst application mode, and calcinations temperature in water environment. A substantial amount of research has focused on the enhancement of TiO2 photocatalysis by modification with metal, non-metal and ion doping. Recent developments in TiO2 photocatalysis for the degradation of various pesticides and phenols are also highlighted in this review. It is evident from the literature survey that photocatalysis has shown good potential for the removal of various organic pollutants. However, still there is a need to find out the practical utility of this technique on commercial scale.