The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe - DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe 2+) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide-rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well-drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.

Influence of medium range transport of particles from nucleation burst on particle number concentration within the urban airshed

An elevated particle number concentration (PNC) observed during nucleation events could play a significant contribution to the total particle load and therefore to the air pollution in the urban environments. Therefore, a field measurement study of PNC was commenced to investigate the temporal and spatial variations of PNC within the urban airshed of Brisbane, Australia. PNC was monitored at urban (QUT), roadside (WOO) and semi-urban (ROC) areas around the Brisbane region during 2009. During the morning traffic peak period, the highest relative fraction of PNC reached about 5% at QUT and WOO on weekdays. PNC peaks were observed around noon, which correlated with the highest solar radiation levels at all three stations, thus suggesting that high PNC levels were likely to be associated with new particle formation caused by photochemical reactions. Wind rose plots showed relatively higher PNC for the NE direction, which was associated with industrial pollution, accounting for 12%, 9% and 14% of overall PNC at QUT, WOO and ROC, respectively. Although there was no significant correlation between PNC at each station, the variation of PNC was well correlated among three stations during regional nucleation events. In addition, PNC at ROC was significantly influenced by upwind urban pollution during the nucleation burst events, with the average enrichment factor of 15.4. This study provides an insight into the influence of regional nucleation events on PNC in the Brisbane region and it the first study to quantify the effect of urban pollution on semi-urban PNC through the nucleation events. © 2012 Author(s).

Vertical particle concentration profiles around urban office buildings

Despite its role in determining both indoor and outdoor human exposure to anthropogenic particles, there is limited information describing vertical profiles of particle concentrations in urban environments, especially for ultrafine particles. Furthermore, the results of the few studies performed have been inconsistent. As such, this study aimed to assess the influence of vehicle emissions and nucleation formation on particle characteristics (particle number size distribution-PNSD and PM 2.5 concentration) at different heights around three urban office buildings located next to busy roads in Brisbane, Australia, and place these results in the broader context of the existing literature. Two sets of instruments were used to simultaneously measure PNSD, particle number (PN) and PM 2.5 concentrations, respectively, for up to three weeks at each building. The results showed that both PNSD and PM 2.5 concentration around building envelopes were influenced by vehicle emissions and new particle formation, and that they exhibited variability across the three different office buildings. During nucleation events, PN concentration in size range of <30 nm and total PN concentration increased (7-65% and 5-46%, respectively), while PM 2.5 concentration decreased (36-52%) with height. This study has shown an under acknowledged role for nucleation in producing particles that can affect large numbers of people, due to the high density and occupancy of urban office buildings and the fact that the vast majority of people's time is spent indoors. These findings highlight important new information related to the previously overlooked role of particle formation in the urban atmosphere and its potential effects on selection of air intake locations and appropriate filter types when designing or upgrading mechanical ventilation systems in urban office buildings. The results also serve to better define particle behaviour and variability around building envelopes, which has implications for studies of both human exposure and particle dynamics. © 2012 Author(s).

Molecular structure of the mineral svanbergite SrAl3(PO 4,SO4)2(OH)6 - A vibrational spectroscopic study

The mineral svanbergite SrAl 3(PO 4,SO 4) 2(OH) 6 is a hydroxy phosphate-sulphate mineral belonging to the beudantite subgroup of alunites and has been characterised by vibrational spectroscopy. Bands at various wavenumbers were assigned to the different vibrational modes of svanbergite, which were then associated with the structure of the mineral. Bands were primarily assigned to phosphate and sulphate stretching and bending modes. Two symmetric stretching modes for both phosphate and sulphate supported the concept of non-equivalent phosphate and sulphate units in the mineral structure. Bands in the OH stretching region enabled hydrogen bond distances to be calculated. Comparison of the hydrogen bond distances and the calculated hydrogen bond distances from the structure models indicates that hydrogen bonding in svanbergite occurs between the two OH units rather than OH to SO42- units.

Raman spectroscopic study of the mineral xonotlite Ca 6Si 6O 17(OH) 2-A component of plaster boards

The mineral xonotlite Ca 6Si 6O 17(OH) 2 is a crystalline calcium silicate hydrate which is widely used in plaster boards and in many industrial applications. The structure of xonotlite is best described as having a dreierdoppelketten silicate structure, and describes the repeating silicate trimer which forms the silicate chains, and doppel indicating that two chains combine. Raman bands at 1042 and 1070 cm -1 are assigned to the SiO stretching vibrations of linked units of Si 4O 11 units. Raman bands at 961 and 980 cm -1 serve to identify Si 3O 10 units. The broad Raman band at 862 cm -1 is attributed to hydroxyl deformation modes. Intense Raman bands at 593 and 695 cm -1 are assigned to OSiO bending vibrations. Intense Raman bands at 3578, 3611, 3627 and 3665 cm -1 are assigned to OH stretching vibrations of the OH units in xonotlite. Infrared spectra are in harmony with the Raman spectra. Raman spectroscopy with complimentary infrared spectroscopy enables the characterisation of the building material xonotlite.

Concentration and oxidative potential of on-road particle emissions and their relationship with traffic composition : Relevance to exposure assessment

Particles emitted by vehicles are known to cause detrimental health effects, with their size and oxidative potential among the main factors responsible. Therefore, understanding the relationship between traffic composition and both the physical characteristics and oxidative potential of particles is critical. To contribute to the limited knowledge base in this area, we investigated this relationship in a 4.5 km road tunnel in Brisbane, Australia. On-road concentrations of ultrafine particles (<100 nm, UFPs), fine particles (PM2.5), CO, CO2 and particle associated reactive oxygen species (ROS) were measured using vehicle-based mobile sampling. UFPs were measured using a condensation particle counter and PM2.5 with a DustTrak aerosol photometer. A new profluorescent nitroxide probe, BPEAnit, was used to determine ROS levels. Comparative measurements were also performed on an above-ground road to assess the role of emission dilution on the parameters measured. The profile of UFP and PM2.5 concentration with distance through the tunnel was determined, and demonstrated relationships with both road gradient and tunnel ventilation. ROS levels in the tunnel were found to be high compared to an open road with similar traffic characteristics, which was attributed to the substantial difference in estimated emission dilution ratios on the two roadways. Principal component analysis (PCA) revealed that the levels of pollutants and ROS were generally better correlated with total traffic count, rather than the traffic composition (i.e. diesel and gasoline-powered vehicles). A possible reason for the lack of correlation with HDV, which has previously been shown to be strongly associated with UFPs especially, was the low absolute numbers encountered during the sampling. This may have made their contribution to in-tunnel pollution largely indistinguishable from the total vehicle volume. For ROS, the stronger association observed with HDV and gasoline vehicles when combined (total traffic count) compared to when considered individually may signal a role for the interaction of their emissions as a determinant of on-road ROS in this pilot study. If further validated, this should not be overlooked in studies of on- or near-road particle exposure and its potential health effects.

Ownership structure and concentration and the timeliness of corporate earnings : Malaysian evidence

This thesis provides the first evidence on how ownership concentration and structure relate to the timeliness of price discovery and reporting lags in Malaysia. Based on a sample of 1,276 Malaysian firms from 1996 to 2009, the results show that ownership concentration and the identity of the largest shareholder matter to the timeliness of price discovery and reporting lags. Specifically, closely-held firms are more timely in their price discovery and have shorter reporting lags, particularly if the largest shareholder is a foreigner or a financial institution. Government-owned firms have longer reporting lags, as expected, but we find no evidence that family-owned firms have significantly different timeliness of price discovery and reporting lags than other firms. Additional analysis shows that prior to the implementation of the Malaysian Code of Corporate Governance, firms were more timely in their price discovery but longer in their reporting lag.

Semi-parametric modelling of ultrafine particle number concentration

Quantifying spatial and/or temporal trends in environmental modelling data requires that measurements be taken at multiple sites. The number of sites and duration of measurement at each site must be balanced against costs of equipment and availability of trained staff. The split panel design comprises short measurement campaigns at multiple locations and continuous monitoring at reference sites [2]. Here we present a modelling approach for a spatio-temporal model of ultrafine particle number concentration (PNC) recorded according to a split panel design. The model describes the temporal trends and background levels at each site. The data were measured as part of the “Ultrafine Particles from Transport Emissions and Child Health” (UPTECH) project which aims to link air quality measurements, child health outcomes and a questionnaire on the child’s history and demographics. The UPTECH project involves measuring aerosol and particle counts and local meteorology at each of 25 primary schools for two weeks and at three long term monitoring stations, and health outcomes for a cohort of students at each school [3].

Airborne concentration of Volatile Organic Compounds in school environment in Brisbane

Traffic emissions are considered as a major source of pollutants, particularly ultrafine particles, in the urban environment. There is an increased concern about airborne particles not only because of their environmental effects but also due to their potential adverse health effects on humans. There have been a number of studies related to the number concentration and size distribution of these particles but studies on the chemical composition of aerosols, especially in the school environment, are very limited. Mejia et. al (2011) reviewed studies on the exposure to and impact of air pollutants on school children and found that there were only a handful of studies on this topic. Therefore, the main focus of this research is on an analysis of the chemical composition of airborne particles, as well as source apportionment and the quantification of ambient concentrations of organic pollutants in the vicinity of schools, as a part of “Ultrafine Particles from Traffic Emissions on Children’s Health” (UPTECH) project. The aim of the present study was to find out the concentrations of different Volatile Organic Compounds (VOCs) in both outdoor and indoor locations from six different schools in Brisbane.

Influence of filtration on I/O particle concentration ratios at urban office buildings

Epidemiological research has consistently shown an association between fine and ultrafine particle concentrations, and increases in both respiratory and cardiovascular morbidity and mortality. These particles, often found in vehicle emissions outside buildings, can penetrate inside via their envelopes and mechanically ventilated systems. Indoor activities such as printing, cooking and cleaning, as well as the movement of building occupants are also an additional source of these particles. In this context, the filtration systems of mechanically ventilated buildings can reduce indoor particle concentrations. Several studies have quantified the efficiency of dry-media and electrostatic filters, but they mainly focused on the particle size range > 300 nm. Some others studied ultrafine particles but their investigations were conducted in laboratories. At this point, there is still only limited information on in situ filter efficiency and an incomplete understanding of filtration influence on I/O ratios of particle concentrations. To help address these gaps in knowledge and provide new information for the selection of appropriate filter types in office building HVAC systems, we aimed to: (1) measure particle concentrations at up and down stream flows of filter devices, as well as outdoor and indoor office buildings; (2) quantify efficiency of different filter types at different buildings; and (3) assess the impact of these filters on I/O ratios at different indoor and outdoor source operation scenarios.

Spatial variation of particle number concentration in school microscale environment

There is significant toxicological evidence of the effects of ultrafine particles (<100nm) on human health (WHO 2005). Studies show that the number concentration of particles has been associated with adverse human health effects (Englert 2004). This work is part of a major study called ‘Ultrafine Particles form Traffic Emissions and Children’s Health’ (UPTECH), which seeks to determine the effect of the exposure to traffic related ultrafine particles on children’s health in schools (http://www.ilaqh.qut.edu.au/Misc/UPT ECH%20Home.htm). Quantification of spatial variation of particle number concentration (PNC) in a microscale environment and identification of the main affecting parameters and their contribution levels are the main aims of this analysis.

Vibrational spectroscopy of the multianion mineral kemmlitzite (Sr,Ce)Al3(AsO4)(SO4)(OH)6

Some minerals are colloidal and show no X-ray diffraction patterns. Vibrational spectroscopy offers one of the few methods for the assessment of the structure of these types of mineral. Among this group of minerals is kemmlitzite (Sr,Ce)Al3(AsO4)(SO4)(OH)6. The objective of this research is to determine the molecular structure of the mineral kemmlitzite using vibrational spectroscopy. Raman microscopy offers a useful method for the analysis of such colloidal minerals. Raman and infrared bands are attributed to the AsO43- , SO42- and water stretching vibrations. The Raman spectrum is dominated by a very intense sharp band at 984 cm-1 assigned to the SO42- symmetric stretching mode. Raman bands at 690, 772 and 825 cm-1 may be assigned to the AsO43- antisymmetric and symmetric stretching modes. Raman bands observed at 432 and 465 cm-1 are attributable to the doubly degenerate 2 (SO4)2- bending mode. Vibrational spectroscopy is important in the assessment of the molecular structure of the kemmlitzite, especially when the mineral is non-diffracting or poorly diffracting.