The surface-structure sensitivity of dioxygen activation in the anatase-photocatalyzed oxidation reaction

The reaction pathways by which oxygen is incorporated into the substrate in the photocatalytic oxidation of terephthalic acid (TPTA) are vastly different on {001} and {101} facets of an anatase single crystal. This was established by controlling the percentage of {101} and {001} facets, isotopically tracing the origins of the hydroxy group, and studying dioxygen consumption and variance in the concentration of hydroxylation intermediate.

Determination of coastal ground and surface water processes and character by use of hydrochemistry and stable isotopes, Fraser Coast, Queensland

This study was part of an integrated project developed in response to concerns regarding current and future land practices affecting water quality within coastal catchments and adjacent marine environments. Two forested coastal catchments on the Fraser Coast, Australia, were chosen as examples of low-modification areas with similar geomorphological and land-use characteristics to many other coastal zones in southeast Queensland. For this component of the overall project, organic , physico-chemical (Eh, pH and DO), ionic (Fe2+, Fe3+), and isotopic (ä13CDIC, ä15NDIN ä34SSO4) data were used to characterise waters and identify sources and processes contributing to concentrations and form of dissolved Fe, C, N and S within the ground and surface waters of these coastal catchments. Three sites with elevated Fe concentrations are discussed in detail. These included a shallow pool with intermittent interaction with the surface water drainage system, a monitoring well within a semi-confined alluvial aquifer, and a monitoring well within the fresh/saline water mixing zone adjacent to an estuary. Conceptual models of processes occurring in these environments are presented. The primary factors influencing Fe transport were; microbial reduction of Fe3+ oxyhydroxides in groundwaters and in the hyporheic zone of surface drainage systems, organic input available for microbial reduction and Fe3+ complexation, bacterial activity for reduction and oxidation, iron curtain effects where saline/fresh water mixing occurs, and variation in redox conditions with depth in ground and surface water columns. Data indicated that groundwater seepage appears a more likely source of Fe to coastal waters (during periods of low rainfall) via tidal flux. The drainage system is ephemeral and contributes little discharge to marine waters. However, data collected during a high rainfall event indicated considerable Fe loads can be transported to the estuary mouth from the catchment.

Influence of organic matter in road deposited particulates in heavy metal accumulation and transport

The research study discussed in the paper investigated the influence of organic matter on heavy metal adsorption for different particle size ranges of build-up solids. Samples collected from road surfaces were assessed for organic matter content, mineral composition, particle size distribution and effective cation exchange capacity. It was found that the organic matter plays a key role in >75µm particles in the adsorption of Zinc, Lead, Nickel and Copper, which are generated by traffic activities. Clay forming minerals and metal oxides of Iron, Aluminium and Manganese was found to be important for heavy metal adsorption to <75µm particles. It was also found that heavy metals adsorbed to organic matter are strongly bound to particles and these metal ions will not be bio-available if the chemical quality of the media remains stable.

Restructuring of carbonaceous particles upon exposure to organic vapours

Recent research has described the restructuring of particles upon exposure to organic vapours; however, as yet hypotheses able to explain this phenomenon are limited. In this study, a range of experiments were performed to explore different hypotheses related to carbonaceous particle restructuring upon exposure to organic and water vapours, such as: the effect of surface tension, the role of organics in flocculating primary particles, as well as the ability of vapours to “wet” the particle surface. The change in mobility diameter (dm) was investigated for a range carbonaceous particle types (diesel exhaust, petrol exhaust, cigarette smoke, candle smoke, particles generated in a heptane/toluene flame, and wood smoke particles) exposed to different organic (heptane, ethanol, and dimethyl sulfoxide/water (1:1 vol%) mixture) and water vapours. Particles were first size-selected and then bubbled through an impinger (bubbler) containing either an organic solvent or water, where particles trapped inside rising bubbles were exposed to saturated vapours of the solvent in the impinger. The size distribution of particles was simultaneously measured upstream and downstream from the impinger. A size-dependent reduction in dm was observed when bubbling diesel exhaust, particles generated in a heptane/toluene flame, and candle smoke particles through heptane, ethanol and a dimethyl sulfoxide/water (1:1 vol %) mixture. In addition, the size distributions of particles bubbled through an impinger were broader. Moreover, an increase of the geometric standard deviation (σ) of the size distributions of particles bubbled through an impinger was also found to be size-dependent. Size-dependent reduction in dm and an increase of σ indicate that particles undergo restructuring to a more compact form, which was confirmed by TEM analysis. However, bubbling of these particles through water did not result in a size-dependent reduction in dm, nor in an increase of σ. Cigarette smoke, petrol exhaust, and wood smoke particles did not result in any substantial change in dm, or σ, when bubbled through organic solvents or water. Therefore, size-dependent reduction in the dm upon bubbling through organic solvents was observed only for particles that had a fractal-like structure, whilst particles that were liquid or were assumed to be spherical did not exhibit any reduction in dm. Compaction of fractal-like particles was attributed to the ability of condensing vapours to efficiently wet the particles. Our results also show that the presence of an organic layer on the surface of fractal-like particles, or the surface tension of the condensed liquid do not influence the extent of compaction.

Indoor and outdoor particle concentrations and elemental and organic carbon at 17 primary schools

The focus of this paper is on the measured particle number concentrations (PNC) as well as elemental and organic carbon in 17 primary schools. This study is part of the “Ultrafine Particles from Traffic Emissions and Children’s Health (UPTECH)”, which aims to determine the relationship between exposure to traffic related ultrafine (UF) particles and children’s health (http://www.ilaqh.qut.edu.au/Misc/UPTECH%20Home.htm). To achieve this, air quality and health data are being collected at 25 schools within Brisbane Metropolitan Area in Australia over two years. This paper presents the general aspects of UF particles data and preliminary results from the first 17 schools (S01 to S17), tested from Oct 2010 to Dec 2011.

The influence of oxygenated organic aerosols (OOA) and its volatile organic content on the oxidative potential of diesel particulate mater

Airborne particulate matter pollution is of concern for a number of reasons and has been widely recognised as an important risk factor to human health. A number of toxicological and epidemiological studies reported negative health effects on both respiratory and cardiovascular system. 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. The production of reactive oxygen species (ROS) has been shown to induce oxidative stress, which is proposed as a mechanism for many of the adverse health outcomes associated with exposure to particulate matter (PM). Therefore, it is crucial to introduce a technique that will allow rapid and routine screenings of the oxidative potential of PM.

Preliminary results on the characterisation of organic aerosols in urban schools by Aerosol Mass Spectrometry

Vehicle emissions have been linked to detrimental health effects with children thought to be more susceptible (See e.g., Ryan et al 2005). In an urban environment a major source of organic aerosols (OA) are vehicle emissions. The ambient concentration of OA is dynamic in nature and the use of an aerosol mass spectrometer can achieve the necessary temporal resolution to capture the daily variation of OA (Jimenez et al 2009). Currently there is a limited understanding of effects of long term exposure to traffic emissions on children’s health. In the present study, we used an aerosol mass spectrometer to monitor OA and determine children’s potential exposure at school to traffic emissions.In this paper, we present the preliminary results of this investigation. The study is a part of a larger project aimed at gaining a holistic picture of the exposure of children to traffic related pollutants, known as UPTECH (www.ilaqh.qut.edu.au/Misc/ UPTECH%20Home.htm).

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.

Diet, physical activity and substrate oxidation : implications for appetite control, weight loss and body composition

In many countries, governments and health agencies are strongly promoting physical activity as a means to prevent the accumulation of fatness that leads to weight gain and obesity. However, there is often a resistance to respond to health promotion initiatives. For example, in the UK, the Chief Medical Officer has recently reported that 71% of women and 61% of men fail to carry out even the minimal amount of physical activity recommended in the government’s guidelines. Similarly, the Food safety Agency has promoted reductions in the intake of fat, sugar and salt but with very little impact on the pattern of consumption. Why is it that recommendations to improve health are so difficult to implement, and produce the desired outcome?

Partitioning of persistent organic pollutants (POPs) between human serum and breast milk : a literature review

The literature was reviewed to assess the relationship between the lipid adjusted concentration in human serum and breast milk (expressed as the serum/milk ratio) of a broad range of POPs in paired samples. Thirteen studies were identified, including seven studies that reported serum/milk ratios for polychlorinated dibenzo-dioxins and -furans (PCDD/Fs), ten for polychlorinated biphenyls (PCBs), five for polybrominated diphenyl ethers (PBDEs), and five for organochlorine pesticides (OCPs). Mean serum/milk ratios ranged between 0.7 and 25 depending on the compound and congener. For PCDD/Fs, PCBs and PBDEs, a clear trend of increasing mean serum/milk ratio by increasing molar volume, hydrophobicity and number of halogen substitutes was observed. The mean serum/milk ratios reported by the 13 studies summarized here will aid comparison between human POPs exposure studies using either serum or milk samples. More studies are needed to allow a valid comparison between data obtained from analysis of breast milk and serum samples for a broader range of POPs. Furthermore such studies may shed light on compound specific factors as well as other determinants that may affect the partitioning and partition kinetics of POPs between serum and breast milk.

Approaches to the Synthesis of a Water-soluble Carboxy Nitroxide

The robust and diversely useful isoindoline nitroxide, 5-carboxy-1,1,3,3-tetramethylisoindolin-2-yloxyl (1; CTMIO), has previously been synthesised in low-to-moderate yields from phthalic anhydride (3). Recent interest in its biological potential as a potent antioxidant and in other areas has seen an increased demand for its production. Herein, three new synthetic routes to CTMIO are presented and their efficiencies assessed. Two routes, via the nitrile 9 and the formyl compound 11, derive from 5-bromo-1,1,3,3-tetramethylisoindoline (6). The third approach starts from the readily accessible starting material, 4-methylphthalic anhydride (12), and proceeds by a methylarene oxidation with potassium permanganate. The three new approaches yield CTMIO in comparable overall yields (16–18 %); however, the synthetic efficiency is most improved when employing the nitrile intermediate 9.

Distribution of organic-rich sediments through the Phanerozoic

It is commonly assumed that rates of accumulation of organic-rich strata have varied through geologic time with some periods that were particularly favorable for accumulation of petroleum source rocks or coals. A rigorous analysis of the validity of such an assumption requires consideration of the basic fact that although sedimentary rocks have been lost through geologic time to erosion and metamorphism. Consequently, their present-day global abundance decreases with their geologic age. Measurements of the global abundance of coal-bearing strata suggest that conditions for coal accumulation were exceptionally favorable during the late Carboniferous. Strata of this age constitute 21% of the world's coal-bearing strata. Global rates of coal accumulation appear to have been relatively constant since the end of the Carboniferous, with the exception of the Triassic which contains only 1.75% of the world's coal-bearing strata. Estimation of the global amount of discovered oil by age of the source rock show that 58% of the world's oil has been sourced from Cretaceous or younger strata and 99% from Silurian or younger strata. Although most geologic periods were favourable for oil source-rock accumulation the mid-Permian to mid-Jurassic appears to have been particularly unfavourable accounting for less than 2% of the world's oil. Estimation of the global amount of discovered natural gas by age of the source rock show that 48% of the world's oil has been sourced from Cretaceous or younger strata and 99% from Silurian or younger strata. The Silurian and Late Carboniferous were particularly favourable for gas source-rock accumulation respectively accounting for 12.9% and 6.9% of the world's gas. By contrast, Permian and Triassic source rocks account for only 1.7% of the world's natural gas. Rather than invoking global climatic or oceanic events to explain the relative abundance of organic rich sediments through time, examination of the data suggests the more critical control is tectonic. The majority of coals are associated with foreland basins and the majority of oil-prone source rocks are associated with rifting. The relative abundance of these types of basin through time determines the abundance and location of coals and petroleum source rocks.