Transition of chromium oxyhydroxide nanomaterials to chromium oxide : a hot stage Raman spectroscopic study

The transition of disc-like chromium hydroxide nanomaterials to chromium oxide nanomaterials has been studied by hot stage Raman spectroscopy. The structure and morphology of α-CrO(OH) synthesised using hydrothermal treatment was confirmed by X-ray diffraction and transmission electron microscopy. The Raman spectrum of α-CrO(OH) is characterised by two intense bands at 823 and 630 cm-1 attributed to ν1 CrIII-O symmetric stretching mode, bands at 1179 cm-1 attributed to CrIII-OH δ deformation modes. No bands are observed above 3000 cm-1. The absence of characteristic OH vibrational bands may be due to short hydrogen bonds in the α-CrO(OH) structure. Upon thermal treatment of α-CrO(OH), new Raman bands are observed at 599, 542, 513, 396, 344 and 304 cm-1, which are attributed to Cr2O3. This hot-stage Raman study shows that the transition of α-CrO(OH) to Cr2O3 occurs before 350 °C.

Transition of synthetic chromium oxide gel to crystalline chromium oxide : a hot stage Raman spectroscopic study

Chromium oxide gel material was synthesised and appeared to be X-ray amorphous. The changes in the structure of the synthetic chromium oxide gel were investigated using hot-stage Raman spectroscopy based upon the results of thermogravimetric analysis. The thermally decomposed product of the synthetic chromium oxide gel in nitrogen atmosphere was confirmed to be crystalline Cr2O3 as determined by the hot-stage Raman spectra. Two bands were observed at 849 and 735 cm-1 in the Raman spectrum at 25 °C, which were attributed to the symmetric stretching modes of O-CrIII-OH and O-CrIII-O. With temperature increase, the intensity of the band at 849 cm-1 decreased, while the band at 735 cm-1 increased. These changes in intensity are attributed to the loss of OH groups and formation of O-CrIII-O units in the structure. A strongly hydrogen bonded water H-O-H bending band was found at 1704 cm-1 in the Raman spectrum of the chromium oxide gel, however this band shifted to around 1590 cm-1 due to destruction of the hydrogen bonds upon thermal treatment. Six new Raman bands were observed at 578, 540, 513, 390, 342 and 303 cm-1 attributed to the thermal decomposed product Cr2O3. The use of the hot-stage Raman microscope enabled low-temperature phase changes brought about through dehydration and dehydroxylation to be studied.

Quantification of the relationship between Fuser Roller Temperature and Laser Printer Emissions

Recently published studies not only demonstrated that laser printers are often significant sources of ultrafine particles, but they also shed light on particle formation mechanisms. While the role of fuser roller temperature as a factor affecting particle formation rate has been postulated, its impact has never been quantified. To address this gap in knowledge, this study measured emissions from 30 laser printers in chamber using a standardized printing sequence, as well as monitoring fuser roller temperature. Based on a simplified mass balance equation, the average emission rates of particle number, PM2.5 and O3 were calculated. The results showed that: almost all printers were found to be high particle number emitters (i.e. > 1.01×1010 particles/min); colour printing generated more PM2.5 than monochrome printing; and all printers generated significant amounts of O3. Particle number emissions varied significantly during printing and followed the cycle of fuser roller temperature variation, which points to temperature being the strongest factor controlling emissions. For two sub-groups of printers using the same technology (heating lamps), systematic positive correlations, in the form of a power law, were found between average particle number emission rate and average roller temperature. Other factors, such as fuser material and structure, are also thought to play a role, since no such correlation was found for the remaining two sub-groups of printers using heating lamps, or for the printers using heating strips. In addition, O3 and total PM2.5 were not found to be statistically correlated with fuser temperature.

Critical analysis of high particle number emissions from accelerating compressed natural gas buses

Compressed natural gas (CNG) engines are thought to be less harmful to the environment than conventional diesel engines, especially in terms of particle emissions. Although, this is true with respect to particulate matter (PM) emissions, results of particle number (PN) emission comparisons have been inconclusive. In this study, results of on-road and dynamometer studies of buses were used to derive several important conclusions. We show that, although PN emissions from CNG buses are significantly lower than from diesel buses at low engine power, they become comparable at high power. For diesel buses, PN emissions are not significantly different between acceleration and operation at steady maximum power. However, the corresponding PN emissions from CNG buses when accelerating are an order of magnitude greater than when operating at steady maximum power. During acceleration under heavy load, PN emissions from CNG buses are an order of magnitude higher than from diesel buses. The particles emitted from CNG buses are too small to contribute to PM10 emissions or contribute to a reduction of visibility, and may consist of semivolatile nanoparticles.

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.

Derivation of motor vehicle tailpipe particle emission factors suitable for modelling urban fleet emissions and air quality assessments

Background, aim, and scope Urban motor vehicle fleets are a major source of particulate matter pollution, especially of ultrafine particles (diameters < 0.1 µm), and exposure to particulate matter has known serious health effects. A considerable body of literature is available on vehicle particle emission factors derived using a wide range of different measurement methods for different particle sizes, conducted in different parts of the world. Therefore the choice as to which are the most suitable particle emission factors to use in transport modelling and health impact assessments presented as a very difficult task. The aim of this study was to derive a comprehensive set of tailpipe particle emission factors for different vehicle and road type combinations, covering the full size range of particles emitted, which are suitable for modelling urban fleet emissions. Materials and methods A large body of data available in the international literature on particle emission factors for motor vehicles derived from measurement studies was compiled and subjected to advanced statistical analysis, to determine the most suitable emission factors to use in modelling urban fleet emissions. Results This analysis resulted in the development of five statistical models which explained 86%, 93%, 87%, 65% and 47% of the variation in published emission factors for particle number, particle volume, PM1, PM2.5 and PM10 respectively. A sixth model for total particle mass was proposed but no significant explanatory variables were identified in the analysis. From the outputs of these statistical models, the most suitable particle emission factors were selected. This selection was based on examination of the statistical robustness of the statistical model outputs, including consideration of conservative average particle emission factors with the lowest standard errors, narrowest 95% confidence intervals and largest sample sizes, and the explanatory model variables, which were Vehicle Type (all particle metrics), Instrumentation (particle number and PM2.5), Road Type (PM10) and Size Range Measured and Speed Limit on the Road (particle volume). Discussion A multiplicity of factors need to be considered in determining emission factors that are suitable for modelling motor vehicle emissions, and this study derived a set of average emission factors suitable for quantifying motor vehicle tailpipe particle emissions in developed countries. Conclusions The comprehensive set of tailpipe particle emission factors presented in this study for different vehicle and road type combinations enable the full size range of particles generated by fleets to be quantified, including ultrafine particles (measured in terms of particle number). These emission factors have particular application for regions which may have a lack of funding to undertake measurements, or insufficient measurement data upon which to derive emission factors for their region. Recommendations and perspectives In urban areas motor vehicles continue to be a major source of particulate matter pollution and of ultrafine particles. It is critical that in order to manage this major pollution source methods are available to quantify the full size range of particles emitted for traffic modelling and health impact assessments.

Carbon dioxide emissions from diesel and compressed natural gas buses during acceleration

Motor vehicle emission factors are generally derived from driving tests mimicking steady state conditions or transient drive cycles. However, neither of these test conditions completely represents real world driving conditions. In particular, they fail to determine emissions generated during the accelerating phase – a condition in which urban buses spend much of their time. In this study we analyse and compare the results of time-dependant emission measurements conducted on diesel and compressed natural gas (CNG) buses during an urban driving cycle on a chassis dynamometer and we derive power-law expressions relating carbon dioxide (CO2) emission factors to the instantaneous speed while accelerating from rest. Emissions during acceleration are compared with that during steady speed operation. These results have important implications for emission modelling particularly under congested traffic conditions.

Development of a composite line source emission model for traffic interrupted microenvironments and its application in particle number emissions at a bus station

A composite line source emission (CLSE) model was developed to specifically quantify exposure levels and describe the spatial variability of vehicle emissions in traffic interrupted microenvironments. This model took into account the complexity of vehicle movements in the queue, as well as different emission rates relevant to various driving conditions (cruise, decelerate, idle and accelerate), and it utilised multi-representative segments to capture the accurate emission distribution for real vehicle flow. Hence, this model was able to quickly quantify the time spent in each segment within the considered zone, as well as the composition and position of the requisite segments based on the vehicle fleet information, which not only helped to quantify the enhanced emissions at critical locations, but it also helped to define the emission source distribution of the disrupted steady flow for further dispersion modelling. The model then was applied to estimate particle number emissions at a bi-directional bus station used by diesel and compressed natural gas fuelled buses. It was found that the acceleration distance was of critical importance when estimating particle number emission, since the highest emissions occurred in sections where most of the buses were accelerating and no significant increases were observed at locations where they idled. It was also shown that emissions at the front end of the platform were 43 times greater than at the rear of the platform. Although the CLSE model is intended to be applied in traffic management and transport analysis systems for the evaluation of exposure, as well as the simulation of vehicle emissions in traffic interrupted microenvironments, the bus station model can also be used for the input of initial source definitions in future dispersion models.

Application of infrared emission spectroscopy to the thermal transition of indium hydroxide to indium oxide nanocubes

Cubic indium hydroxide nanomaterials were obtained by a low temperature soft-chemical method without any surfactants. The transition of nano-cubic indium hydroxide to cubic indium oxide during dehydroxylation has been studied by infrared emission spectroscopy. The spectra are related to the structure of the materials and the changes in the structure upon thermal treatment. The infrared absorption spectrum of In(OH)3 is characterised by an intense OH deformation band at 1150 cm-1 and two O-H stretching bands at 3107 and 3221 cm-1. In the infrared emission spectra, the hydroxyl-stretching and hydroxyl-bending bands diminish dramatically upon heating, and no intensity remains after 200 °C. However, new low intensity bands are found in the OH deformation region at 915 cm-1 and in OH stretching region at 3437 cm-1. These bands are attributed to the vibrations of newly formed InOH bonds because of the release and transfer of protons during calcination of the nanomaterial. The use of infrared emission spectroscopy enables the low-temperature phase transition brought about through dehydration of In(OH)3 nanocubes to be studied.

Fast hole surface conduction observed for indoline sensitizer dyes immobilized at fluorine-doped tin oxide - TiO2 surfaces

The indoline dyes D102, D131, D149, and D205 have been characterized when adsorved on fluorine-doped tin oxide (FTO) and TiO2 electrode surfaces. Adsorption from 50:50 acetonitrile - tert-butanol onto flourine-doped tin oxide (FTO) allows approximate Langmuirian binding constants of 6.5 x 10(4), 2.01 x 10(3), 2.0 x 10(4), and 1.5 x 10(4) mol-1 dm3, respectively, to be determined. Voltammetric data obtained in acetonitrile/0.1 M NBu4PF6 indicate reversible on-electron oxidation at Emid = 0.94, 0.91, 0.88, and 0.88 V vs Ag/AgCI(3 M KCI), respectively, with dye aggregation (at high coverage) causing additional peak features at more positive potentials. Slow chemical degradation processes and electron transfer catalysis for iodine oxidation were observed for all four oxidezed indolinium cations. When adsorbed onto TiO2 nanoparticle films (ca. 9nm particle diameter and ca.3/um thickness of FTO0, reversible voltammetric responses with Emid = 1.08, 1.156, 0.92 and 0.95 V vs Ag/AgCI(3 M KCI), respectively, suggest exceptionally fast hole hopping diffusion (with Dapp > 5 x 10(-9) m2 s-1) for adsorbed layers of four indoline dyes, presumably due to pie-pie stacking in surface aggregates. Slow dye degradation is shown to affect charge transport via electron hopping. Spectrelectrochemical data for the adsorbed indoline dyes on FTO-TiO2 revealed a red-shift of absorption peaks after oxidation and the presence of a strong charge transfer band in the near-IR region. The implications of the indoline dye reactivity and fast hole mobility for solar cell devices are discussed.

Towards low emissions in the electricity generation sector : creating a coherent legal model for Australia

Australia’s efforts to transition to a low-emissions economy have stagnated following the successive defeats of the Carbon Pollution Reduction Scheme. This failure should not, however, be regarded as the end of Australia’s efforts to make this transition. In fact, the opportunity now exists for Australia to refine its existing arrangements to enable this transition to occur more effectively. The starting point for this analysis is the legal arrangements applying to the electricity generation sector, which is the largest sectoral emitter of anthropogenic greenhouse gas emissions in Australia. Without an effective strategy to mitigate this sector’s contribution to anthropogenic climate change, it is unlikely that Australia will be able to transition towards a low-emissions economy. It is on this basis that this article assesses the dominant national legal arrangement – the Renewable Energy Target – underpinning the electricity generation sector's efforts to become a low-emissions sector.

Carbon financing and the Australian emissions trading scheme : less emissions, more opportunities?

The introduction by the Australian federal government of its Carbon Pollution Reduction Scheme was a decisive step in the transformation of Australia into a low carbon economy. Since the release of the Scheme, however, political discourse relating to environmental sustainability and climate change in Australia has focused primarily on political, scientific and economic issues. Insufficient attention has been paid to the financial opportunities which commoditisation of the carbon market may offer, and little emphasis has been placed on the legal implications for the creation of a "new" asset and market. This article seeks to shed some light on the discernable opportunities which the Scheme should provide to participants in the Australian and international debt markets.